KR20070086613A - Phenothizines, s-oxides, and s,s-dioxides as well as phenoxazines as emitters for oleds - Google Patents

Abstract

Disclosed is the use of phenoxazine derivatives, phenothiazine derivatives, phenothiazine-S oxide or phenothiazine-S,S dioxide derivatives as emitter substances or hole and exciton blockers in organic light-emitting diodes. The invention further relates to an organic light-emitting diode comprising a light-emitting layer that contains at least one phenoxazine derivative, phenothiazine derivative, phenothiazine-S oxide or phenothiazine-S,S dioxide derivative as an emitter substance, as well as a light-emitting layer which contains or is composed of said phenoxazine derivative, phenothiazine derivative, phenothiazine-S oxide or phenothiazine-S,S dioxide derivative as an emitter substance, a hole and exciton blocking layer that contains or is composed of said phenoxazine derivative, phenothiazine derivative, phenothiazine-S oxide or phenothiazine-S,S dioxide derivative, as well as a device comprising an inventive organic light-emitting diode. The invention finally relates to special phenothiazine-S,S dioxide derivatives, phenothiazine-S oxide derivatives, and phenothiazine derivatives, a method for the production thereof, and the use thereof in organic light-emitting diodes.

Description

Phenothiazines, S-oxides, S, S-oxides, and phenoxazines as emitters for OLEDs

The present invention relates to phenoxazine derivatives, phenothiazine derivatives, phenothiazine S-oxide derivatives or phenothiazine S, S- as emitter materials or hole and exciton blockers in organic light emitting diodes. Use of a dioxide derivative, an organic light emitting diode comprising a light emitting layer, the light emitting layer comprising at least one phenoxazine derivative, phenothiazine derivative, phenothiazine S-oxide derivative or phenothiazine S, S- as an emitter material An organic light emitting diode comprising a dioxide derivative, and the above-mentioned phenoxazine derivative, phenothiazine derivative, phenothiazine S-oxide derivative or phenothiazine S, S-dioxide derivative as the emitter material or A light emitting layer composed of the derivative, the aforementioned phenoxazine derivative, phenothiazine derivative, phenothiazine S-oxide derivative or phenothiazine S, S-dioxide derivative And exciton-blocking layer and a hole configured Accordingly, the present invention relates to a device comprising an organic light emitting diode of the present invention. The present invention also relates to specific phenothiazine S, S-dioxide derivatives, phenothiazine S-oxide derivatives and phenothiazine derivatives and methods for their preparation, and their use in organic light emitting diodes.

In organic light-emitting diodes (OLEDs), the property of the material to emit light when the material is excited by an electric current is used. OLEDs are particularly interesting as an alternative to liquid crystal displays and cathode ray tubes for the manufacture of flat visual display units. Because of the very compact design and inherently low electricity consumption, devices comprising LEDs are particularly suitable for mobile applications, for example in mobile phones, laptops and the like.

A number of materials have been proposed that emit light upon excitation by electric current.

According to the prior art, phenoxazine and phenothiazine derivatives are generally used as charge transport materials.

EP-A 0 517 542, for example, is known for its excellent thermal stability and relates to aromatic amino compounds which may have units comprising phenothiazine units. Such aromatic amino compounds are used as hole transport materials in OLEDs.

Likewise, EP-A 0 562 883 relates to a hole transport material with high thermal stability used in OLEDs. The hole transport material used is a trisfenthiathiazinyltriphenylamine derivative or a trisphenoxazinyltriphenylamine derivative.

DE-A 101 43 249 relates to a process for the production of conjugated oligo- and polyphenothiazines and their use as hole conductors in organic light emitting diodes and field-effect transistors. Oligo- and polyphenothiazines are prepared by cross coupling of functionalized phenothiazine derivatives.

EP-A 0 535 672 discloses an electrophotographic phot or eceptor comprising an organic conductive material in the photosensitive layer. Suitable organic conductive materials include compounds having phenothiazine structural units.

US 5,942,615 and JP-A 11-158165 relate to electrophotographic photosensitive members comprising phenothiazine and phenoxazine derivatives, as charge transport materials comprising these derivatives, and the disclosed charge transport materials. Phenothiazine or phenoxazine derivatives are derivatives of the formula:

Wherein Ar ¹ and Ar ² are each an aryl group, R ¹ and R ² are each H, lower alkyl or aryl, R ³ is lower alkyl, an alicyclic hydrocarbon radical having 5 to 7 carbon atoms, aryl or Aralkyl, X is S or O, and m and n are each 0 or 1. With regard to the luminescence of the above-mentioned compounds, in particular electric field luminescence, neither US 5,942,615 nor JP-A 11-158165 contain any information.

The prior art discloses only some very specific phenothiazine and phenoxazine derivatives used as luminescent materials in the light emitting layer of OLEDs.

JP-A 2003-007466 relates to an OLED comprising a polymer having a long lifetime, high illumination density and having repeating units based on phenothiazine or phenoxazine derivatives as luminescent materials.

JP-A 2000-328052 relates to a luminescent material which is formed from a monocyclic or fused polycyclic compound which emits in the electromagnetic spectrum in the yellow to red region and has two specific substituents. These specific substituents are substituents of the formula:

In the above formula,

B is S or O,

R ¹ is H, alkyl or aryl,

R ² and R ³ are each independently H, CN, halogen, alkylcarbonyl and alkoxycarbonyl; R ² and R ³ are each preferably CN.

Phenothiazine and phenoxazine derivatives are referred to as fused polycyclic compounds.

KR 2003-0029394 relates to a red luminophore suitable for organic field emission. These luminophores have a phenocyanidin group excellent in hole transport properties and an anthracenyl radical excellent in electron transport ability. Depending on the substitution pattern of the chromophores, they can represent the electromagnetic spectrum of the green region as well as the yellow and red regions. The particular chromophore has one of the following formulas:

Wherein R ¹ and R ² radicals may be H, aryl, heteroaryl, halogen or saturated or unsaturated hydrocarbons. A particular feature of the compounds to be emphasized is that they have not only luminescent properties but also hole transport properties and electron transport properties by their special substitution pattern.

JP-A 2004-075750 relates to phenoxazine derivatives of the formula:

Wherein R ₁ is an aromatic or aliphatic bonding group and R ₂ is an alkyl, alkenyl, alkyl ether, alkoxy, amino, aryl or aryloxy group. Phenoxazine derivatives are used as fluorescent materials in the light emitting layer of OLEDs.

Summary of the Invention

It is an object of the present application to provide additional emitter materials, in particular blue light emitting materials, for use in OLEDs, which are readily obtainable and have excellent illumination density and quantum yield when used in OLEDs, preferably matrix materials It can be used in materials in the light emitting layer in OLEDs without incorporation into them. A further object of the present application is to provide materials suitable as hole and exciton blockers.

This object is achieved by using compounds of the general formula (I) as emitter materials in organic light-emitting diodes, in particular materials which emit in the blue region of the electromagnetic spectrum, or as hole and exciton blockers:

In the above formula,

X is S, SO ₂ , O, SO, preferably S or SO ₂ , more preferably SO ₂ ;

R ¹ is H, alkyl, aryl, heteroaryl, preferably H, methyl, ethyl, unsubstituted phenyl or 4-alkoxyphenyl; or

A group of formula IV or formula V;

R ² , R ³ are each independently H, alkyl, aryl, NR ²² R ²³ or COR ³¹ , wherein R ² and R ³ are simultaneously H, preferably H or aryl, more preferably H, unsubstituted phenyl Is not 1-naphthyl or 2-naphthyl, or

At least one of the R ² or R ³ radicals is a radical of the formula (II) wherein the further R ² or R ³ radicals have the same definition or are H, alkyl, aryl, NR ²² R ²³ , preferably H, NR ²² R ²³ or aryl, most preferably H, NPh ₂ or unsubstituted phenyl, preferably further R ² or R ³ radicals are likewise radicals of formula II, or

One of the R ² or R ³ radicals is a radical of formula III wherein the further R ² or R ³ radicals are H, alkyl, aryl, NR ²² R ²³ , preferably H, NR ²² R ²³ or aryl, most Preferably H, NPh ₂ or unsubstituted phenyl;

R ⁴ , R ⁵ , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ are Each independently is alkyl, aryl, alkenyl, alkynyl or alkylaryl, preferably alkyl or aryl;

R ¹⁷ is halogen, alkoxy, alkyl, aryl, alkenyl, alkynyl or alkylaryl, preferably fluorine, alkoxy, alkyl or aryl;

m, n are each 0, 1, 2 or 3, preferably 0 or 1, more preferably 0;

o, p, q, r, s, t, u, v, w are each 0, 1, 2, 3 or 4, preferably 0 or 1, more preferably 0;

z is 1 or 2, preferably 1;

R ⁶ , R ⁷ are each independently H, alkyl, aryl, alkenyl, alkynyl, alkylaryl, alkoxy, aryloxy or NR ²² R ²³ , preferably H, alkyl or aryl, more preferably alkyl or aryl , Most preferably methyl or unsubstituted phenyl;

R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are each independently H, alkyl, aryl, alkenyl, alkynyl or alkylaryl, preferably H, alkyl or aryl, more preferably H or alkyl, most preferred Preferably H;

R ¹² is H, alkyl or aryl, preferably H, methyl, ethyl, unsubstituted phenyl or 4-alkoxyphenyl;

R ²² , R ²³ are each independently H, alkyl, aryl, preferably aryl, or

R ²² and R ²³ together form a cyclic radical, preferably a 5- or 6-membered radical;

Y, Z, W are each S, SO ₂ , O, SO, preferably S or SO ₂ ;

Ar is arylene, preferably phenylene, naphthylene or biphenylene;

R ³¹ is H, alkyl or aryl.

The emitter materials of formula (I) used according to the invention are readily obtainable and have excellent illumination density and quantum yield when used in OLEDs. The emitter material of formula (I) is particularly famous as an emitter material with good illumination properties even when used as a material in the emitting layer of an OLED, ie when used without a matrix material. For this reason, inconvenient vacuum evaporation with the matrix material is not necessary at all for the application of the emitting layer of the OLED. Therefore, the manufacturing process of the OLED having the emitter material of formula (I) used according to the present invention can be carried out inexpensively.

In addition, the compounds of formula (I) can be used as hole and exciton blockers in organic light emitting diodes.

Alkyl, alkenyl and alkynyl radicals and also alkyl radicals of the alkoxy groups are, according to the present application, linear, branched, cyclic and / or optionally substituted with substituents selected from the group consisting of aryl, alkoxy, NR ²² R ²³ and halogen. Wherein R ²² and R ²³ are as defined above.

Suitable halogen substituents are fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine, more preferably fluorine and chlorine.

Suitable aryl substituents are specified below. Alkyl, alkenyl and alkynyl radicals are preferably unsubstituted.

Examples of suitable alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl. This includes both the n- and branched isomers of the radicals, for example isopropyl, isobutyl, isopentyl, sec-butyl, tert-butyl, neopentyl, 3,3-dimethylbutyl and the like. Preferred alkyl groups are methyl and ethyl.

Cyclic alkyl radicals (cycloalkyl radicals) represent cycloalkyl and also cycloalkylalkyl (alkyl substituted with cycloalkyl), wherein cycloalkyl has at least three carbon atoms. Examples of cycloalkyl radicals are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. If appropriate, they can also be polycyclic ring systems, for example decarinyl, norbornanyl, bornanyl or adamantyl. Cycloalkyl radicals may be unsubstituted or optionally substituted with one or more additional radicals listed above as examples for the alkyl radicals.

Examples of alkenyl and alkynyl groups include vinyl, 1-propenyl, 2-propenyl (allyl), 2-butenyl, 2-methyl-2-propenyl, 3-methyl-2-butenyl, ethynyl, 2-propynyl (propargyl), 2-butynyl or 3-butynyl.

Suitable alkoxy groups have the general formula -OR ²⁴ , wherein R ²⁴ is an alkyl radical as defined above. Suitable alkoxy substituents are selected from the group consisting of OCH ₃ , OC ₂ H ₅ , OC ₃ H ₇ and OC ₄ H ₉ . In this regard, C ₃ H ₇ and C ₄ H ₉ include n- and branched isomers such as isopropyl, isobutyl, sec-butyl and tert-butyl. Especially preferred are methoxy and ethoxy. R ²⁴ may also be an aralkyl radical such as benzyl or phenylethyl.

In the present invention, aryl refers to radicals derived from monocyclic or bicyclic aromatics which do not contain ring heteroatoms. If this radical is not a monocyclic system, the saturated form (perhydro form) or partially unsubstituted form (e.g. dihydro form or tetrahydro form) is the term aryl as long as the specific form is known and stable. It is also possible in the second ring. This means that the term aryl herein also includes, for example, bicyclic radicals in which either radical is aromatic or bicyclic radicals in which only one ring is aromatic. Examples of aryl are phenyl, naphthyl, indanyl, 1,2-dihydronaphthenyl, 1,4-dihydro or ptenyl, indenyl or 1,2,3,4-tetrahydronaphthyl. Aryl is more preferably phenyl or naphthyl, most preferably phenyl. Ph in the context of the present application means phenyl.

Aryl radicals may be unsubstituted or substituted with one or more additional radicals. Suitable further radicals are selected from the group consisting of alkyl, aryl, alkoxy, NR ²² R ²³ and halogen. In addition, suitable radicals formula OC (O) R ³² -, where, R ³² is H, alkyl or aryl, preferably aryl, more preferably phenyl carbonyloxy Im - with those of the formula OR ³³ - where, R ³³ Are radicals of H, alkyl or aryl, preferably H, and heteroaryl radicals and aryloxy radicals. The definitions of preferred alkyl, aryl, alkoxy and halogen radicals, heteroaryl radicals and aryloxy radicals, and R ²² , R ²³ radicals are already specified above. The aryl radicals are preferably unsubstituted or substituted with one or more alkoxy groups. Aryl is more preferably unsubstituted phenyl or 4-alkoxyphenyl. Aryl is most preferably unsubstituted phenyl.

Heteroaryl refers to heteroaryl radicals different from the aryl radicals described above in that at least one carbon atom in the basic skeleton of the aryl radical has been replaced by a heteroatom. Preferred heteroatoms are N, O and S. Very particular preference is given to the substitution of one, two or three carbon atoms of the basic skeleton of the aryl radical with a heteroatom. This base skeleton is particularly preferably pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, cyclic esters, cyclic amides and 5-membered heteroaromatics such as triazolyl, imidazolyl, pyra Systems such as zolyl, thienyl, pyrrolyl and furyl, and fusion systems such as benzimidazolyl. The base skeleton may be substituted at one of the substitutable positions of the base skeleton, a plurality of said positions, or both. Suitable substituents are the same as those already specified for aryl.

Suitable aryloxy groups have the general formula -OR ²⁵ , wherein R ²⁵ is an aryl radical as defined above. Especially preferred is phenoxy.

According to the present application, arylene represents a phenylene, naphthylene or biphenylene group which may be unsubstituted or substituted with the substituents specified for the aryl radical. The arylene group is preferably unsubstituted. Preferred phenylene groups are 1,3- or 1,4-phenylene, particularly preferred are 1,4-phenylene; Preferred naphthylene groups are 1,5-, 1,6-, 2,6- or 2,7-naphthylene, preferred are 1,5- or 2,6-naphthylene; Preferred biphenylene groups are 4,4'-biphenylene.

Suitable amino groups have the formula NR ²² R ²³ , wherein R ²² and R ²³ are each independently H, alkyl or aryl, preferably aryl. R ²² and R ²³ may also form cyclic radicals, preferably 5- or 6-membered cyclic radicals, together with the nitrogen atoms of the amino groups. It may also contain nitrogen atoms as well as additional heteroatoms selected from N, O and S.

In a preferred embodiment, the invention relates to the use of the emitter material or hole and exciton blocker of formula (I), wherein the symbols and radicals are each defined as follows:

X is S or SO ₂ , preferably SO ₂ ;

R ¹ is H, methyl, ethyl, unsubstituted phenyl or 4-alkoxyphenyl, or one OH, OC (O) Ph, OCH ₂ Ph or N-phenyl-benzimidazolyl group, three CH ₃ groups or 2 Phenyl or pyridyl substituted with F radicals; or

A group of formula IV or formula V;

Formula IV

Formula V

R ² , R ³ are each H, unsubstituted phenyl, 1-naphthyl, 2-naphthyl or NR ²² R ²³ or CHO, wherein at least one of the R ² or R ³ radicals is unsubstituted phenyl, 1-naph Til, 2-naphthyl or NR ²² R ²³ or CHO, or

R ² and R ³ are each a group of formula II, or

Formula II

R ² is H and R ³ is a group of formula III;

Formula III

m, n, o, p, q, r, s, t, u, v and w are each 0, 1 or 2, preferably 0;

z is 1 or 2, preferably 1;

R ⁶ and R ⁷ are each unsubstituted phenyl;

R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are each H;

R ¹² is H, methyl, ethyl, unsubstituted phenyl or 4-alkoxyphenyl or phenyl substituted with three CH ₃ groups;

R ¹⁷ is alkyl, alkoxy, preferably methoxy;

R ²² and R ²³ are each aryl;

Y, Z, W are each S or SO ₂ , preferably SO ₂ ;

Ar is phenylene, naphthylene or biphenylene.

The emitter material of formula (I) is more preferably selected from the group consisting of compounds of formula (Ia), (Ib), (Ic), (Id), (Ie) If and Ig:

In the above formula,

X, Y, Z, W, Q are each independently S or SO ₂ , preferably SO ₂ ;

R ¹ , R ¹² are each H, methyl, ethyl or unsubstituted phenyl;

R ² , R ³ are each H or unsubstituted phenyl, wherein at least R ² or R ³ is unsubstituted phenyl;

R ⁶ is methyl or unsubstituted phenyl;

R ¹⁷ is methoxy;

s is 0 or 2, wherein when s = 2 the substituents are preferably arranged in 2- and 5-positions;

Ph is unsubstituted phenyl.

The compounds of formulas (Ia), (Ib) and (Ic) are more preferably symmetric, that is, R ² and R ³ in the compounds of formula (Ia) are more preferably the same, and the R ⁶ radicals of both of the compounds of formula (Ib) are more Preferably the same, in the compounds of formula (Ic) R ¹ and R ¹² and X and Y are preferably the same; X and Z in the compounds of formulas Id and Ie are more preferably the same, X and W in the compounds of formula If are more preferably the same, and X, Z and Q in the compounds of formula Ig are more preferably the same Do.

In a further preferred embodiment, the emitter material of formula I is selected from the group consisting of compounds of formulas Ih and Ii:

In the above formula,

X and Y are each independently S or SO ₂ , preferably SO ₂ ;

R ¹ is phenyl substituted with one OH, OC (O) Ph, OCH ₂ Ph or N-phenylbenzimidazolyl group, three CH ₃ groups or two F radicals, 4-methoxyphenyl, thienyl or Pyridyl;

R ² is H;

R ³ is H or CHO, preferably H,

R ¹² is phenyl substituted with three CH ₃ groups.

Preferred compounds of formula (I) for use as hole and exciton blockers are selected from the group consisting of compounds of formula (Ia), (Id), (Ie), (Ig) and (Ih); More preferably, the hole and exciton blockers are selected from compounds of formulas Ia and Ih.

Phenoxazine, phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives of the above-mentioned formula (I) used according to the invention may be prepared by methods known to those skilled in the art. .

Compounds of formula (I) wherein X, Y, Z, W and Q are each S or O are suitable for the commercially available phenoxazine or phenothiazine base skeletons wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each H It can be prepared by substitution. When the R ² , R ³ , R ⁴ and R ⁵ radicals are not H, the R ² , R ³ , R ⁴ and R ⁵ radicals are introduced by electrophilic aromatic substitution. Suitable reaction conditions are known to those skilled in the art. If the R ¹ radical is not H, the radical is introduced by electrophilic substitution on nitrogen, for example by reaction with a suitable alkyl or aryl halide. In a further preferred embodiment, the base skeleton is functionalized, for example halogenated or functionalized with aldehyde groups. The functionalized backbone is then reacted with a suitable compound with R ² , R ³ , R ⁴ and R ⁵ radicals by coupling or Wittig reactions to produce the desired phenoxazine or phenothiazine.

Alternatively, the compounds of formula (I) start from already functionalized building blocks suitable for the preparation of phenoxazine derivatives, phenothiazine derivatives, phenothiazine S-oxide derivatives or phenothiazine S, S-dioxide derivatives It can also manufacture. For example, the phenoxazine derivatives used according to the invention can also be prepared by heating o-aminophenols functionalized with R ² and R ⁴ radicals together with their hydrochloride functionalized with R ³ and R ⁵ radicals. Functionalized building blocks are prepared by methods known to those skilled in the art. The phenothiazine derivatives used according to the invention can also be prepared starting from diphenylamine derivatives functionalized with R ² , R ³ , R ⁴ and R ⁵ radicals by heating with sulfur. The preparation of functionalized diphenylamine derivatives is known to those skilled in the art.

Preference is given to preparing compounds of formula (I) for use according to the invention starting from the commercially available phenoxazine and phenothiazine base skeletons.

Compounds of formula (I) wherein X is SO ₂ or SO are prepared, for example, by oxidation of the corresponding functionalized phenothiazine. Suitable methods for oxidizing phenothiazine to phenothiazine S-oxide and phenothiazine S, S-dioxide are known to those skilled in the art and described, for example, in M. Tosa et al. Heterocyclic Communications, Vol. 7, No. 3, 2001, p. 277-282.

Phenothiazine oxidation of S- oxide derivatives, for example, ethanol or ethanol-acetone mixture of _{H 2 O 2, H 2 O} 2, and ammonium sulfate, nitrate, nitrite, inorganic nitrogen oxide, NO ₂ / O of oxalic acid _2, NO ⁺ BF ₄ ^- it is performed by / O _2, CrO ₃ in pyridine, ozone, tetramethyl oxirane, by alkyl oxazol geographic Dean perfluoroalkyl, or electrochemical method. In addition, suitably functionalized phenothiazines of formula (I) are prepared by the m-chloroperbenzoic acid in CH ₂ Cl ₂ or by a mixture of glacial acetic acid and fuming nitric acid in CCl ₄ at a temperature of 0 to 5 ° C. It can be oxidized with phenoxazine S-oxide derivatives (see, eg, M. Tosa et al. Heterocyclic Communications, Vol. 7, No. 3, 2001, p. 277-282).

Oxidation to phenothiazine S, S-dioxide derivatives is for example peracetic acid formed from peracids, for example H ₂ O ₂ and AcOH, or m-chloroperbenzoic acid, sodium perborate, NaOCl or heavy metal systems, for example _{KMnO 4 / H 2 O, Et} 3 PhN + MnO 4 - is carried out by such as morpholine N- oxide-of the organic medium -, OsO ₄ / N- methyl. For example, suitably functionalized phenothiazines of Formula (I) can be prepared by an aqueous solution of C ₁₆ H ₃₅ N (CH ₃ ) ₃ ⁺ Cl ^- and KMnO ₄ in CHCl ₃ at room temperature, or in CH ₂ Cl ₂ at room temperature. m-chloroperbenzoic acid can be oxidized to the corresponding phenothiazine S, S-dioxide derivatives of formula (I) (see, eg, M. Tosa et al. Heterocyclic Communications, Vol. 7, No. 3). , 2001, p. 277-282).

For the preparation of phenothiazine S, S-dioxide derivatives wherein X is SO ₂ , the phenothiazine derivatives and oxidizing agents, preferably m-chloroperbenzoic acid, are generally 1: 1.8 to 1: 4, preferably 1 It is used in a molar ratio of 1: 1.9 to 1: 3.5, more preferably 1: 1.9 to 1: 3.

For the preparation of phenothiazine S-oxide derivatives wherein X is SO, phenothiazine derivatives and oxidizing agents are generally used in molar ratios of 1: 0.8 to 1: 1.5, preferably 1: 1 to 1: 1.3. Oxidizing agents, such as H ₂ O ₂ , which do not cause further oxidation to the corresponding S, S-dioxide derivatives, may be used in excess of those specified above in connection with phenothiazine derivatives.

Oxidation is generally carried out in a solvent, preferably a halogenated hydrocarbon such as methylene chloride and a solvent selected from the group consisting of double polar aprotic solvents such as acetonitrile or sulfolane.

In general, oxidation to phenothiazine S-oxide derivatives is carried out at temperatures of -10 ° C to + 50 ° C, preferably -5 ° C to + 30 ° C, more preferably 0 ° C to + 20 ° C. Typically, this oxidation is done at standard pressure. The reaction time of this oxidation is generally 0.25 to 24 hours, preferably 1 to 15 hours, more preferably 2 to 10 hours.

Oxidation to phenothiazine S, S-dioxide derivatives is generally carried out at temperatures of +0 to + 100 ° C. Typically, this oxidation is done at standard pressure.

In a preferred embodiment, the phenothiazine S-oxide derivative of formula (I) is oxidized at 0 to 20 ° C. by oxidizing the corresponding phenothiazine derivative of formula (I) with m-chloroperbenzoic acid in CH ₂ Cl ₂ as oxidant. Are manufactured.

Phenothiazine S, S-dioxide derivatives of formula (I) are prepared by oxidizing the corresponding phenothiazine derivatives of formula (I) using m-chloroperbenzoic acid in CH ₂ Cl ₂ as oxidizing agent at 0-40 ° C.

The resulting phenothiazine S-oxides and phenothiazine S, S-dioxides are isolated and worked up by methods known to those skilled in the art.

The preparation of the compounds of the formula (I) used according to the invention is carried out by a process for the preparation of the compounds of the formulas (Ia), (Ib), (Ic), (Id), (Ie), (If) and (Ig), which are preferably used by way of example, It will be illustrated below with reference to. Based on this information, and using the knowledge of the prior art, those skilled in the art are in a position to prepare additional compounds for use in accordance with the present invention.

a) Preferred Formulas Used Ia  And Ih Preparation of the compound

Compounds of formula (Ia) and (Ih) which are preferably used are, for example, starting from the basic skeleton of formula (VI)

Wherein X is S or SO ₂

aa) N-alkylation or N-arylation of the basic skeleton of formula VI,

ab) halogenation, and

ac) coupling reactions with precursor compounds corresponding to the desired R ² and R ³ radicals;

ad) where appropriate, oxidation when X = S

Is manufactured by

Step aa) is carried out only when R ¹ is not H.

Suitable reaction conditions for carrying out steps aa), ab), ac) and ad) are known to those skilled in the art. Preferred embodiments of steps aa), ab), ac) and ad) are specified below.

Step aa)

N-alkylation or N-arylation preferably represents the basic skeleton of formula VI wherein R ¹ -Hal, wherein R ¹ is already defined above and Hal is Cl, Br or I, preferably By reaction with an alkyl halide or an aryl halide.

N-alkylation or N-arylation is carried out in the presence of a base. Suitable bases are known to those skilled in the art and are preferably alkali metal and alkaline earth metal hydroxides such as NaOH, KOH, Ca (OH) ₂ , alkali metal hydrides such as NaH, KH, alkali metals Amides such as NaNH ₂ , alkali metal or alkaline earth metal carbonates such as K ₂ CO ₃ , and alkali metal alkoxides such as NaOMe, NaOEt. Also suitable are mixtures of the aforementioned bases. Especially preferred are NaOH, KOH or NaH.

N-alkylation (for example disclosed in M. Tosa et al., Heterocycl. Communications, Vol. 7, No. 3, 2001, p. 277-282) or N-arylation (eg H. Gilman and DA Shirley, J. Am. Chem. Soc. 66 (1944) 888; disclosed in D. Li et al., Dyes and Pigments 49 (2001) 181-186) Preferably in a solvent. Suitable solvents are, for example, polar aprotic solvents such as dimethyl sulfoxide, dimethylformamide or alcohols. Likewise, it is possible to use excess alkyl or aryl halides used as solvent, with preference being given to using excess alkyl or aryl iodide. Additionally this reaction may be carried out in a nonpolar aprotic solvent such as toluene in the presence of a phase transfer catalyst such as tetra-n-butylammonium hydrogensulfate (see, for example, I. Gozlan et. al., J. Heterocycl. Chem. 21 (1984) 613-614).

N-arylation may also be effected, for example, by copper-catalyzed coupling of a compound of formula VI with an aryl halide, preferably aryl iodide (Ullmann reaction). Suitable N-arylation methods of phenothiazine in the presence of copper bronze are described, for example, in H. Gilman et al., J. Am. Chem. Soc. 66 (1944) 888-893.

The molar ratio of the compound of formula VI to the alkyl halide or aryl halide of the formula R ¹ -Hal is generally from 1: 1 to 1: 2, preferably from 1: 1 to 1: 1.5.

N-alkylation or N-arylation is generally carried out at temperatures of 0 to 220 ° C, preferably 20 to 200 ° C. The reaction time is generally 0.5 to 48 hours, preferably 1 to 24 hours. Generally, N-alkylation or N-arylation is carried out at standard pressure.

The resulting crude product is worked up by methods known to those skilled in the art.

If R ^{1 in} the compound of formula (Ia) is H, step aa) is not necessary.

Step ab)

Halogenation can be carried out by methods known to those skilled in the art. Preference is given to bromination or iodinating at the 3- and 7-positions of the basic structure of the formula VI, either N-alkylated or N-arylated, as appropriate.

Where appropriate, the basic structure of N-alkylated or N-arylated formula VI in step aa) is described, for example, in M. Jovanovich et al. J. Org. Chem. 1984, 49, 1905-1908 may be brominated in 3- and 7-positions of the base skeleton by reaction with bromine in acetic acid. Bromination is also described in C. Bodea et al. Acad. Rep. Rom. 13 (1962) 81-87.

Where appropriate, the basic backbone of Formula VI, either N-alkylated or N-arylated in step aa) is described, for example, in M. Sailer et al. J. Org. Chem. 2003, 68, 7509-7512 may be iodinated at the 3- and 7-positions of the base skeleton. In this method, the N-alkylated or N-arylated corresponding 3,7-dibromo-substituted base skeleton of the formula VI is lithiated first and the lithiated product is then iodized if appropriate.

Lithiation is a method known to those skilled in the art and generally n-butyllithium and lithium diisopropylamide at temperatures of -78 to + 25 ° C, preferably -78 to 0 ° C, more preferably -78 ° C. It may be carried out using a lithium base selected from the group consisting of. The reaction mixture is then warmed to room temperature and worked up by methods known to those skilled in the art.

Step ac)

The phenothiazine derivatives of formula (Ia) used according to the invention are preferably prepared by coupling reactions with precursor compounds corresponding to the desired R ² and R ³ radicals. Suitable coupling reactions are, for example, Suzuki coupling and Yamamoto coupling, with Suzuki coupling being preferred.

In Suzuki coupling, the halogenated, in particular brominated, compounds at the 3 and 7 positions of the phenothiazine base skeleton of the formula VI, if appropriate, N-alkylated or N-arylated, are desired under the Pd (0) catalyst in the presence of a base. It may also be reacted with a boric acid or boric acid ester corresponding to the R ² and R ³ radicals to produce the corresponding 3,7-R ² , R ³ -substituted compounds.

It is also possible to use the desired R ² and R ³ radicals or the corresponding acid instead of the boric acid ester, other boron compounds having the desired R ² and R ³ radicals from the reaction between the halogenated phenothiazine derivative in. The boron compound is a cyclic compound of the formula R ² -B (-O- [C (R ²⁷ ) ₂ ] _n -O-) and R ³ -B (O)-[C (R ²⁷ ) ₂ ] _n -O-). compound, where, R ² and R ³ each of R ² and a have the definitions set forth with respect to R ^3, R ²⁷ are the same or different hydrogen or a C ₁ -C ₂₀ - and alkyl, such as methyl, ethyl example, n- Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl , sec-hexyl, n-heptyl, isoheptyl, n-octyl, n-decyl, n-dodecyl or n-octadecyl; Preferably C ₁ -C ₁₂ -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl , Neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl or n-decyl, more preferably C ₁ -C ₄ -alkyl, for example methyl, ethyl, n- Propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, most preferably methyl; n is an integer of 2-10, Preferably it is 2-5.

Boric acid, boric acid esters and boron compounds corresponding to the desired R ² and R ³ radicals can be prepared or commercially available by the methods disclosed in the prior art. For example, it is possible to prepare boric acid and boric acid esters by reacting Grignard or lithium reagents with borane, diborane or borate.

Suitable Pd (0) catalysts are all conventional Pd (0) catalysts. For example, it is possible to use tris (dibenzylideneacetone) dipalladium (0) or tetrakis (triphenyl-phosphine) palladium (0). It is also possible to use Pd (II) salts in the form of mixtures with ligands, for example Pd (ac) ₂ or PdCl ₂ and PPh ₃ , where Pd (0) is formed in situ so that coupling takes place, Excess PPh ₃ may be added. The catalyst is generally used in an amount of 0.001 to 15 mol%, preferably 0.01 to 10 mol%, more preferably 0.1 to 5 mol%, based on the halogenated phenothiazine derivative used.

In Suzuki coupling, all bases conventionally used in Suzuki coupling can be used. Preference is given to using alkali metal carbonates such as sodium carbonate or potassium carbonate. The base is generally used in molar excess of from 2 to 200 times, preferably from 2 to 100 times, more preferably from 2 to 80 times, based on the halogenated phenothiazine derivatives used.

The components corresponding to the desired R ² and R ³ radicals (boric acid, corresponding boric acid esters or other suitable boron compounds) are 100 to 400 mol%, preferably 100 to 300 mol%, more preferably relative to the halogenated phenothiazine derivatives. Is used in a ratio of 100 to 150 mol%.

This reaction is generally carried out at a temperature of 40 to 140 ° C, preferably 60 to 120 ° C, more preferably 70 to 100 ° C. Pressure is generally standard pressure.

This reaction is generally carried out excluding oxygen. Typically this reaction is carried out in a solvent selected from the group consisting of benzene, toluene, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, ethanol and petroleum ether. Similarly, it is possible to use tetrahydrofuran, dimethoxyethane or a mixture of ethanol and water as the solvent.

In an advantageous variant of this process, the halogenated phenothiazine derivatives are initially charged in solution under protective gas, and the base is preferably present in dissolved form, for example in a mixture of dimethoxyethane / water. And boric acid corresponding to the desired R ² and R ³ radicals. The Pd (0) catalyst is then added under protective gas. The mixture is stirred at the aforementioned temperatures and pressures generally over 3 to 120 hours, preferably 4 to 72 hours, more preferably 6 to 48 hours. The reaction mixture is then worked up by methods known to those skilled in the art.

The phenothiazine derivatives of formula (Ia) used according to the invention may also be prepared in addition to Suzuki coupling by other methods known to those skilled in the art, in particular by other coupling reactions.

In a further embodiment of the invention, the phenothiazine derivatives of the formula (Ia) of the invention, where appropriate, have a basic skeleton of N-alkylated or N-arylated formula VI and are halogenated in the 3 and 7 positions, in particular brominated The resulting phenothiazine is obtained by reacting a halogen compound, in particular a bromine compound, corresponding to the desired R ² and R ³ radicals under a Ni (0) catalyst (Yamamoto coupling).

In a preferred embodiment of the Yamamoto coupling, a solution of the catalyst, preferably a DMF solution, is prepared from equimolar amounts of Ni (0) compounds, preferably Ni (COD) ₂ , and bipyridyl with the exclusion of oxygen. . With the exclusion of oxygen, halogenated, preferably brominated phenothiazine derivatives and bromine compounds corresponding to the desired R ² and R ³ radicals-in solvents, preferably in toluene-are added to the solution.

In the preparation of the phenothiazine derivatives of formula (Ia) by Yamamoto coupling, the reaction conditions correspond to, for example, temperature, pressure, solvent and halogenated, preferably brominated phenothiazine derivatives versus R ² and R ³ The ratio of the compound to be corresponds to that of Suzuki coupling.

Suitable Ni (0) compounds for the preparation of catalysts are all conventional Ni (0) compounds. For example, Ni (C ₂ H ₄ ) ₃ , Ni (1,5-cyclooctadiene) ₂ (“Ni (COD) ₂ ”, Ni (1,6-cyclodecadiene) ₂ or Ni (1,5 It is possible to use, 9-all-trans-cyclododecatrienes _{2. The} catalyst is 1 to 100 mol%, preferably 5 to 80 mol, based on the halogenated phenothiazine derivative used. %, More preferably in an amount of 10 to 70 mol%.

Process conditions and catalysts which are particularly suitable for Suzuki coupling are described, for example, in Suzuki-Miyaura cross-coupling: A. Suzuki, J. Organomet. Chem. 576 (1999) 147-168; See B-Alkyl Suzuki-Miyaura cross-coupling: S.R. Chemler et al., Angew. Chem. 2001, 113, 4676-4701 and the documents cited therein.

Step ad)

Preferred oxidizing agents and process conditions for the oxidation of phenothiazines corresponding to phenothiazine S, S-dioxide derivatives are specified above and described, for example, in M. Tosa et al., Heterocyclic Commun. 7 (2001) 277-282.

b) Formulas preferably used Ib Preparation of the compound

Compounds of formula (Ib) which are preferably used are, for example, starting from the basic skeleton of formula (VI)

Formula VI

(Wherein X is S or SO ₂ )

ba) N-alkylation or N-arylation of the base skeleton of formula VI, wherein step ba) is carried out only when R ¹ is not H;

bb) conversion of the resulting compound to bisaldehyde of formula VII,

bc) reaction of a bisaldehyde of formula VII with an alkylphosphonic acid ester of formula VIII,

Wherein R ²⁶ is C ₁ -to C ₆ -alkyl

Is prepared by obtaining a phenothiazine of formula (Ib) which is symmetrical, ie R ⁶ is in each case Me or unsubstituted Ph.

One of R ⁶ is Me and one asymmetric compound of formula b is unsubstituted Ph, for example, step bc) from the formula (VIII) of the alkyl phosphonic acid esters of one molar equivalent of the bis aldehyde of the formula VII - wherein, R ⁶ is Me-followed by 1 molar equivalent of alkylphosphonic acid ester of formula VIII, wherein R ⁶ is Ph-followed by 1 molar equivalent of alkylphosphonic acid ester of formula VIII, wherein R ⁶ is Me It may also be obtained.

In addition, the Vilsmeier-Haack reaction (see, eg, NP Buu-Hoi, N. Hoan, J. Chem. Soc. 1951, 1834-1836) or L. Gaina et al. , Heterocycl.Commun. 7 (2001), 549-554) to prepare a monoaldehyde, which is equivalent to 1 molar equivalent of alkylphosphonic acid ester of formula VIII, wherein R ⁶ is Ph or It is also possible to obtain an asymmetric compound of formula (Ib) by reacting with Me. This produces a compound of formula IX wherein X and R ¹ are as defined for formula Ib, respectively, and R ⁶ is Ph or Me:

The resulting compound is then subjected to further Vilsmeier-Hack reactions (eg NP Buu-Hoi, N. Hoan, J. Chem. Soc. 1951, 1834-1836) or L. Gaina et al. , Heterocycl. Commun. 7 (2001 ), to sikineunde by 549-554] method disclosed in) switch to the aldehyde of formula X, X and R ¹ in the formula X are as defined with respect to formula (Ib), respectively, R ⁶ is It is Ph or Me:

The aldehyde of formula (X) is reacted with one molar equivalent of alkylphosphonic acid ester of formula (VIII), wherein R ⁶ in Formula (VIII) is Ph or Me and R ⁶ is different from the R ⁶ radical already present in the aldehyde of Formula (X).

bd) Where appropriate, oxidation of the phenothiazine derivative of formula (Ib) to the corresponding phenothiazine S, S-oxide derivative of formula (Ib)

Suitable oxidants and process conditions are specified above and are described, for example, in M. Tosa et al., Heterocyclis Commun. 7 (2001) 277-282.

Alternatively, step bb) is followed by first oxidizing to the corresponding phenothiazine S, S-dioxide derivative (step bd), followed by subsequent reaction with an alkylphosphonic acid ester of formula VIII (step bc) It is possible.

Suitable reaction conditions for carrying out steps ba), bb) and bc) are known to those skilled in the art. Preferred embodiments of steps ba), bb) and bc) are specified below.

step ba )

The N-alkylation or N-arylation of the basic skeleton of the formula (VI) in step ba) preferably corresponds to the process for the preparation of the compound of formula (Ia) already described in step aa).

Step bb)

Suitable processes for carrying out step bb) in the preparation of symmetric bisaldehydes are described, for example, in US Pat. No. 5,942,615 and in H. Pat. Oelschlager and HJ Peters, Arch. Pharm. (Weinheim) 320 (1987) 379-381. When the reaction product from the bis aldehyde is preferably a step of formula VII ba) a (R ¹ is H when the R ¹ other than H, when used), suitable compounds of formula VI POCl ₃ and a Lewis acid (Lewis acid) or Br? nsted acid, for example ZnCl ₂ , by reaction with formamide, for example N, N-dimethylformamide or N-methylformanilide. Preferred is described in H. Oelschlager and HJ Peters, Arch. Pharm. (Weinheim) 320 (1987) 379-381 to prepare bisaldehyde.

Suitable processes for carrying out step bb) in the preparation of monoaldehydes which can be used for the preparation of asymmetric compounds of formula (lb) are described, for example, in N.P. Buu-Hoi, N. Hoan, J. Chem. Soc. 1951, 1834-1836 and L. Gaina et al., Heterocycl. Commun. 7 (2001), 549-554. For example, monoaldehydes, if appropriate, can be used with N-alkylated or N-arylated phenothiazine base skeletons of formula VI, in the absence of solvent (generally in excess of formamide in this case) or formamide in o-dichlorobenzene. For example by reacting with N-methylformanilide or N, N-dimethylformamide, phosphorus oxychloride.

The reaction can be carried out in an organic solvent such as toluene, xylene, chlorobenzene, o-dichlorobenzene (for monoaldehydes) or acetonitrile (for bisaldehydes).

Step bc)

Suitable processes for carrying out step bc) are disclosed, for example, in US Pat. No. 5,942,615. Bisaldehyde of formula (VII) is preferably reacted with alkylphosphonic acid ester of formula (VIII) in the presence of a base.

Suitable bases are, for example, hydroxides such as NaOH, KOH, amides such as sodium amides, hydrides such as NaH, KH, and metal alkoxides such as NaOMe, NaOtBu, KOtBu.

The reaction can be carried out in a solvent. Suitable solvents are alcohols such as methanol, ethanol, ethers such as 1,2-dimethoxyethane, diethyl ether, tetrahydrofuran or dioxane, hydrocarbons such as toluene or xylene, polar aprotic Solvents such as dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide or N-methylpyrrolidone, or mixtures of the solvents mentioned.

The molar ratio between the bisaldehyde of formula (VII) and the alkylphosphonic acid ester of formula (VIII) is generally 1: 2 in the preparation of symmetric compounds of formula (Ib), ie compounds in which R ⁶ is in each case Ph or in each case Me. When preparing an asymmetric compound of Formula (Ib) wherein one R ⁶ is Me and the other is unsubstituted Ph, the reaction first utilizes 1 molar equivalent of an alkylphosphonic acid ester of Formula VIII wherein R ⁶ is Me, followed by R ⁶ 1 molar equivalent of alkyl phosphonic acid ester of formula VIII is Ph, or first 1 molar equivalent of alkylphosphonic acid ester of formula VIII is R ⁶ is Ph, followed by 1 molar equivalent of formula R ⁶ is Me It is performed using the alkyl phosphonic acid ester of VIII. This means that the molar ratio between the bisaldehyde of formula VII and the alkylphosphonic acid ester of formula VIII is generally 1: 1. The resulting compound is then reacted with a molar ratio of 1: 1 with an equivalent molar equivalent of alkylphosphonic acid ester and first alkylphosphonic acid ester and other further phosphonic acid esters, based on the compounds already reacted.

When monoaldehydes are reacted with alkylphosphonic acid esters of formula (VII) to prepare compounds of formula (IX), the monoaldehydes and alkylphosphonic acid esters are generally reacted in a molar ratio of 1: 1. Further reaction of the compound of formula (IX) to produce a compound of formula (X) and subsequently to an asymmetric compound of formula (Ic) is done according to steps bb) and bc). The required molar ratio of the components used can be readily determined by one skilled in the art.

The molar ratio of base to alkylphosphonic acid esters used is generally from 1: 1 to 1: 2, preferably from 1: 1.1 to 1: 1.5.

The reaction temperature is generally 0 ° C to 150 ° C, preferably 20 ° C to 80 ° C. The reaction time is generally 0.5 to 24 hours, preferably 1 to 10 hours. Typically, the reaction is carried out at standard pressure.

Alkylphosphonic acid esters are prepared, for example, by heating the corresponding aralkyl chlorides or mixtures of bromide and trialkyl phosphites in substance or in a solvent such as toluene or xylene.

step bd )

The oxidation of phenothiazine of formula (Ib) to the corresponding phenothiazine S, S-dioxide has already been described above. Suitable oxidants and process conditions are specified above and are described, for example, in M. Tosa et al., Heterocyclic Commun. 7 (2001) 277-282.

Alternatively, after step bb) it is possible to first oxidize to the corresponding phenothiazine S, S-dioxide (step bd) and then to react with the alkylphosphonic acid ester of formula VIII (step bc).

c) Preferred Formulas Used Ic  And preparation of compounds of Ii

Compounds of formula (Ic) and (Ii) which are preferably used are likewise starting from the basic skeleton of formula (VI)

Formula VI

Wherein X is S or SO ₂

ca) N-alkylation or N-arylation of the base skeleton of formula VI, wherein step ca) is carried out only when R ¹ and R ¹² are not H;

cb) The resulting compound was subjected to a Vilsmeier-Hack reaction (see, eg, NP Buu-Hoi and N. Hoan, J. Chem. Soc. 1951, 1834-1836, Gaina et al., Heterocycl Commun. 7 (2001), 549-554) or H. Oelschlager and H.J. Peters, Arch. Pharm. (Weinheim) 320 (1987) 379-381, which converts monoaldehydes of the general formula (XIa) or XIb:

cc) reacting a compound of formula (XIa) and a compound of formula (XIb) with a phosphonic acid ester of formula (XII) to obtain a phenothiazine derivative of formula (Ic),

Wherein R ²⁷ is C ₁ -to C ₆ -alkyl

cd) Where appropriate, oxidation of the phenothiazine derivative of formula (Ic) to the corresponding phenothiazine S, S-dioxide

Is prepared by.

Alternatively, the phenothiazine derivative having an aldehyde group and obtained in step cb) may be converted to the corresponding phenothiazine S, S-dioxide derivative (step cc '). This phenothiazine S, S-dioxide derivative is then converted to the desired phenothiazine S, S-dioxide derivative of the formula (Ic) by reaction of the phosphoric ester of formula (XII) (step cd ').

Reaction conditions suitable for carrying out steps ca), cb), cc), cd), cc ') and cd') are known to those skilled in the art. Preferred embodiments of steps ca), cb), cc), cd), cc ') and cd') are specified below.

Step ca)

N-alkylation or N-arylation of the basic backbone of formula VI in step ca) preferably corresponds to the process already described in step aa) for the preparation of compounds of formula la. In N-alkylation or N-arylation with R ¹² radicals, instead of alkyl halides or aryl halides of formula R ¹ -Hal, alkyl halides or aryl halides of formula R ¹² -Hal are otherwise steps in the preparation of formula (Ia). It is used under the same reaction conditions as described in aa).

Step cb)

Step cb) is for example described in the preparation of the corresponding aldehydes in H. Oelschlager and HJ Peters, Arch. Pharm. (Weinheim) 320 (1987) 379-381 or in US 5,942,615 and in NP Buu-Hoi and N. Hoan, J. Chem. Soc. 1951, 1834-1836, Gaina et al., Heterocycl. Commun. 7 (2001), 549-554, it may be carried out similarly to the process disclosed in. N-alkylated or N-arylated compounds having a basic backbone of formula VI and obtained after step ca), or analogous compounds in which the nitrogen atom is substituted with an R ¹² radical, are in the presence of POCl ₃ and, if appropriate, Lewis acid or Briggs Preference is given to reacting with formamide, for example N, N-dimethylformamide or N-methyl-formanilide, in the presence of tedic acid, for example ZnCl ₂ . If R ¹ or R ¹² is H, the compound of formula VI is reacted directly in step cb) and step ca) is not necessary.

Preferred reaction conditions in step cb) correspond to the reaction conditions disclosed in step bb) in the preparation of bisaldehyde of formula VII.

The molar ratio of the N-alkylated or N-arylated compound obtained in step ca), or the compound of formula VI to formamide when R ¹ or R ¹² is H, is generally from 1: 1 to 1: 5, preferably 1 : 1 to 1: 2.

The molar ratio of the N-alkylated or N-arylated compounds obtained in step ca), or compounds of formula VI and POCl ₃ when R ¹ or R ¹² is H, is generally from 1: 1 to 1: 2, preferably 1 : 1 to 1: 1.5.

The molar ratio of the N-alkylated or N-arylated compounds obtained in step ca), or compounds of formula VI and Lewis or Bronsted acids, when R ¹ or R ¹² is H, is generally from 1: 1 to 1: 1.5 , Preferably 1: 1 to 1: 1.2.

Step cc)

When the compounds of formula (XIa) and (XIb) are identical, a symmetric compound of formula (Ic) is obtained. For the different compounds of formulas IXa and IXb, compounds of formula Ic are obtained which are asymmetric.

For the preparation of symmetrical compounds of formula (Ic), compounds of formula (XIa) or XIb are reacted with phosphonic acid esters of formula (XII). In the preparation of symmetrical compounds of formula (Ic) the molar ratio between the aldehyde of formula (XIa) or XIb and the alkylphosphonic acid ester of formula (XII) is generally about 2: 1.

For the preparation of asymmetric compounds of formula (Ic), the aldehyde of formula (XIa) (or XIb) is first reacted with a phosphonic acid ester of formula (XII). The molar ratio between the aldehyde of formula (XIa) (or XIb) and the alkylphosphonic acid ester of formula (XII) is generally about 1: 1. The resulting compound is then reacted with an aldehyde of formula (XIb) (or XIa), which is different from the first aldehyde, to give an asymmetric compound of formula (Ic).

The reaction conditions in the reaction of the aldehyde with the alkylphosphonic acid ester correspond to the reaction conditions specified in step bc).

As disclosed in US Pat. No. 3,984,399, alkylphosphonic acid esters of formula (XII) are reacted by reacting the corresponding dichloride or dibromide of formula (XIII) with trialkyl phosphite, in the form of a substance, or Are manufactured.

Wherein Hal is Cl or Br

Step cd)

For the preparation of phenothiazine S, S-dioxide derivatives of formula (Ic), phenothiazine derivatives of formula (Ic) are oxidized. Suitable oxidants and process conditions have already been specified above, see for example M. Tosa et al. Heterocyclic Commun. 7 (2001) 277-282. It should be taken into account that the two sulfur atoms in the phenothiazine derivative of formula (Ic) are oxidized to the corresponding S, S-dioxide. Thus, the molar ratio of phenothiazine derivatives of formula (Ic) to phenothiazine S, S-dioxide derivatives of formula (Ic), wherein X and Y are each SO ₂ , is generally from 1: 3.8 to 1: 8, preferably Is 1: 3.9 to 1: 6.

Alternatively for steps cc) and cd), the phenothiazine S, S-dioxide derivative of formula (Ic) may be obtained by step cc ') and cd') after step cb).

Step cc ')

For the preparation of phenothiazine S, S-dioxide derivatives, the aldehydes of formulas XIa and / or XIb, wherein X is S, may be subjected to oxidation. This oxidation is carried out corresponding to the process specified in step ad).

Step cd ')

After step cc ′), the resulting phenothiazine S, S-dioxide derivatives of Formulas XIa and / or XIb are reacted with phosphonic acid esters of Formula XII to obtain phenothiazine S, S-dioxide derivatives of Formula Ic can do. Changes in suitable conditions and processes of the reaction with phosphonic acid esters of formula (XII) correspond to changes in the conditions and processes specified in step cc).

d) Preparation of Preferred Compounds of Formula (Id)

Preferred compounds of the formula Id are prepared, for example, by the following method. 1,3-dihalobenzene, preferably 1,3-diiodobenzene is generally 1.8 to 2.2 molar equivalents, preferably 2 molar equivalents, in the presence of copper powder and alkali metal carbonate, preferably potassium carbonate Together with phenothiazine, phenothiazine S-oxide or phenothiazine S, S-oxide, it is generally heated to 160-220 ° C. and maintained at this temperature for 8-48 hours. The reaction mixture is cooled to approximately 140 ° C. and ethyl acetate is added and the mixture is heated to boiling for about 1 hour under reflux. Work up can be performed by the following steps, for example. The solution is filtered hot and, after cooling, mixed with alcohol, preferably methanol. The precipitate is filtered off with suction, dried and then recrystallized.

In the above reactions, compounds of formula Id are formed in which X and Z have the same definition. For the preparation of compounds of formula (Id) in which X and Z have different definitions, first, 0.9 to 1.1 molar equivalents of 1,3-dihalobenzene, preferably 1 molar equivalent of phenothiazine, phenothiazine S-oxide Or reacted with phenothiazine S, S-dioxide, and then the resulting compound is 0.9 to 1.1 molar equivalents different from the first phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide It is possible to react, preferably with 1 molar equivalent of additional phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide.

Similarly, compounds of formula (Id) generally contain 1.8 to 2.2 molar equivalents, preferably 2 molar equivalents of 1,3-difluorobenzene, of NaH-deprotonated phenothiazine, phenothiazine S-oxide or It is possible to convert by reacting with notthiazine S, S-dioxide.

In the above reactions, compounds of formula Id are formed in which X and Z have the same definition. For the preparation of compounds of formula (Id) in which X and Z have different definitions, first, 0.9 to 1.1 molar equivalents, preferably 1 molar equivalent, of NaH-deprotonated phenothiazine, pe React with notthiazine S-oxide or phenothiazine S, S-dioxide, and the resulting compound is then subjected to the first deprotonated phenothiazine, phenothiazine S-oxide or phenothiazine S, S- Reacting with an additional 0.9 to 1.1 molar equivalent, preferably 1 molar equivalent, of NaH-deprotonated phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide different from the dioxide It is possible.

e) chemical formula Ie Preparation of Preferred Compounds

Preferred compounds of formula (Ie) are prepared, for example, by the following methods. 1,4-dihalobenzene, preferably 1,4-diiodobenzene is generally 1.8 to 2.2 molar equivalents, preferably 2 molar equivalents, in the presence of copper powder and alkali metal carbonate, preferably potassium carbonate Together with phenothiazine, phenothiazine S-oxide or phenothiazine S, S-oxide, it is generally heated to 160-220 ° C. and maintained at this temperature for 8-48 hours. The reaction mixture is cooled to approximately 100 ° C., hot water is added and the mixture is heated to boiling for about 1 hour under reflux. Work up can be performed by the following steps, for example. The solution is filtered hot. The residue is cooled and then boiled in methylene chloride for about 1 hour under reflux. After cooling to room temperature, the suspension is filtered. The filtrate is chromatographed on silica gel in methylene chloride.

In the above reactions, compounds of formula (Ie) are formed in which X and Z have the same definition, corresponding to the preparation of compounds of formula (Id). For the preparation of compounds of formula (Ie) in which X and Z have different definitions, first, 0.9 to 1.1 molar equivalents of 1,4-dihalobenzene, preferably 1 molar equivalent of phenothiazine, phenothiazine S-oxide Or reacted with phenothiazine S, S-dioxide, and then the resulting compound is 0.9 to 1.1 molar equivalents different from the first phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide It is possible to react, preferably with one molar equivalent of additional phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide.

Similarly, compounds of formula (Ie) can be converted by reacting 1,4-difluorobenzene with NaH-deprotonated phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide Do. Symmetric (X and Z have the same definition) and asymmetric compounds of formula (Ie) can be prepared corresponding to the preparation of compounds of formula (Id).

f) Preparation of Preferred Compounds of Formula If

Compounds of formula If can be obtained in a manner corresponding to compounds of formula Ie.

g) Preparation of Preferred Compounds of Formula (Ig)

Preferred compounds of formula (Ig) are prepared, for example, by methods according to the following: 1,3,5-trifluorobenzene, generally 2.8 to 3.2 molar equivalents, preferably 3 molar equivalents of NaH-deprotonation Reaction with phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide. Work up is done by methods known to those skilled in the art.

In the above reactions, compounds of formula (Ig) are formed in which each of X, Z and Q has the same definition. Compounds of formula (Ig) in which X, Z and Q have different definitions sequentially convert 1,3-trifluorobenzene to different NaH-deprotonated phenothiazines, phenothiazine S-oxides or phenothiazine S, S May be caused by reacting with dioxide.

Phenoxazine, phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives of the formula I used according to the invention are suitable for use in OLEDs. These derivatives are used as emitter materials in OLEDs because they can exhibit luminescence (field emission) in the visible region of the electromagnetic spectrum, preferably in the blue region of the electromagnetic spectrum. In the context of the present application, electric field luminescence represents both electric field fluorescence and electric field phosphorescence. In a further embodiment of the invention, the compounds of formula (I) are used as hole or exciton blockers in OLEDs.

The aforementioned compounds of formula (I) are markedly suitable for use as emitter materials or hole or exciton blockers in organic light emitting diodes (OLEDs). Accordingly, the present invention also provides an organic light emitting diode comprising a light emitting layer comprising or consisting of at least one emitter material of formula (I). Preferred phenoxazine, phenothiazine, phenothiazine S-oxides or phenothiazine S, S-dioxide derivatives of formula I have already been specified above. The present invention also provides an organic light emitting diode comprising a blocking layer for holes and excitons, comprising or consisting of at least one compound of formula (I). Preferred compounds of formula (I) are mentioned above.

Organic light emitting diodes (OLEDs) are formed in principle from a plurality of layers, for example:

1. Anode

2. Hole transport layer

3. Light emitting layer

4. electron transport layer

5. cathode

Layer sequences that differ from the structures specified above and known to those skilled in the art are also possible. For example, it is possible for OLEDs to have some of the layers mentioned, for example OLEDs with layers 1 (anode), layers 3 (light emitting layers) and layers 5 (cathodes) are likewise suitable. In this case, the functions of the layer 2 (hole transport layer) and the layer 4 (electron transport layer) are assumed by the adjacent layer. OLEDs having layers (1), (2), (3) and (5) or having (1), (3), (4) and (5) are likewise suitable.

Phenoxazine, phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives of formula I are used as emitter molecules in the emissive layer. Accordingly, the present application also provides a light emitting layer comprising at least one emitter material of formula (I) according to the present application.

The present invention also provides an organic light emitting diode (OLED) comprising a blocking layer of holes and excitons, wherein the blocking layers of holes and excitons comprise at least one compound of formula (I).

Phenoxazine, phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives of the formula I used according to the invention may be present in the emissive layer in the form of a material without further additives. have. However, in addition to the phenoxazine, phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives used according to the invention, it is likewise possible that additional compounds are present in the emitting layer. For example, a fluorescent dye may be present for changing the emission color of the compound of formula (I) used as emitter molecule. Diluent material may also be present. Such diluent material may be a polymer, for example poly (N-vinylcarbazole) or polysilane. However, the diluent material may also be a small molecule such as 4,4'-N, N'-dicarbazolebiphenyl (CBP = CDP) or tertiary aromatic amine. When a diluent material is used, the proportion of phenoxazine, phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide derivative of the formula I used in accordance with the invention in the light emitting layer is generally 20% by weight. Less than%, preferably from 0.5 to 10% by weight. In one embodiment of the invention, phenoxazine, phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives of the formula (I) used according to the invention are used in substance form, This avoids costly and inconvenient coevaporation of the compound of formula (I) with the matrix material (diluent material or fluorescent dye). For this purpose, it is essential for the phenoxazine, phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide derivative of formula I to emit light in the solid state. The compounds of formula (I) used according to the invention exhibit luminescence in the solid state. Thus, the light emitting layer comprises, in one embodiment, at least one phenoxazine, phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide derivative of Formula I, and a diluent material and a fluorescent It contains no matrix material selected from dyes. Especially preferred are light emitting layers consisting of at least one emitter material of formula (I).

The individual aforementioned layers of the OLED may in turn be composed of two or more layers. For example, the hole transport layer may be composed of one layer into which holes are injected from the electrode and one layer to transport holes from the hole injection layer into the light emitting layer. The electron transport layer may likewise be composed of a plurality of layers, for example, one layer in which electrons are injected by an electrode and one layer that receives electrons from the electron injection layer and transports them into the light emitting layer. These layers are each selected according to factors such as energy level, thermal resistance and charge carrier mobility and also energy differences of the layers mentioned in the organic layer or metal electrode. One skilled in the art can select the structure of the OLED in such a way that it will be optimally adapted to the organic compound used as the emitter material according to the present invention.

In order to obtain particularly efficient OLEDs, the HOMO (highest occupied molecular orbital) of the hole transport layer should be aligned with the work function of the anode and the LUMO (lowest unoccupied) of the electron transport layer molecular orbital) must be aligned to the work function of the cathode.

The present application also provides an OLED comprising at least one light emitting layer of the invention comprising or consisting of at least one emitter material of formula (I). Additional layers in the OLED are typically used for such layers and may be composed of any materials known to those skilled in the art.

The anode 1 is an electrode that provides a positive charge carrier. This anode may for example be composed of a material comprising a metal, a mixture of different metals, a metal alloy, a metal oxide or a mixture of different metal oxides. Alternatively, the anode can be a conductive polymer. Suitable metals include metals of groups Ib, IVa, Va and VIa of the Periodic Table of Elements, and also transition metals of Group VIIIa. When the anode should be transparent, mixed metal oxides of Group IIb, IIIb and IVb of the Periodic Table of the Elements (formerly IUPAC version), for example indium tin oxide (ITO), are generally used. Likewise, Nature, Vol. 357, pages 477 to 479 (June 11, 1992), it is possible for the anode 1 to comprise an organic material, for example polyaniline. At least one of the anode or the cathode must be at least partially transparent in order to be able to emit the light formed.

Suitable hole transport materials for layer (2) of the inventive OLED are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pages 837 to 860, 1996. Either hole transport molecule or polymer may be used as the hole transport material. Commonly used hole transport molecules are 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD), N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (TPD), 1,1-bis [(di-4-tolylamino) -phenyl] -cyclohexane (TAPC) , N, N'-bis (4-methylphenyl) -N, N'-bis (4-ethylphenyl)-[1,1 '-(3,3'-dimethyl) -biphenyl] -4,4'- Diamine (ETPD), tetrakis- (3-methylphenyl) -N, N, N ', N'-2,5-phenylenediamine (PDA), α-phenyl-4-N, N-diphenyl-amino- Styrene (TPS), p- (diethylamino) benzaldehyde diphenylhydrazone (DEH), triphenylamine (TPA), bis [4- (N, N-diethylamino) -2-methylphenyl)] (4- Methylphenyl) methane (MPMP), 1-phenyl-3- [p- (diethylamino) styryl] -5- [p- (diethylamino) phenyl] -pyrazoline (PPR or DEASP), 1,2- Trans-bis (9H-carbazol-9-yl) cyclobutane (DCZB), N, N, N ', N'-tetrakis (4-methylphenyl)-(1,1'-biphenyl) -4,4 '-Diamine (TTB), 4', 4 ', 4 "-tris (N, N-diphenylamino) triphenyla Min (TDTA) and porphyrin compounds, and also phthalocyanine, for example copper phthalocyanine, hole transport polymers commonly used are selected from the group consisting of polyvinylcarbazole, (phenylmethyl) polysilane and polyaniline Likewise, it is possible to obtain hole transporting polymers by doping hole transporting molecules into polymers such as polystyrene and polycarbonates Suitable hole transporting molecules are the molecules already mentioned above.

Layers (4) DP of the OLEDs of the invention Suitable electron transporting materials are based on metals chelated with an oxynoid compound, for example compounds based on tris (8-quinolinolato) -aluminum (Alq3), phenanthroline For example 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA = BCP) or 4,7-diphenyl-1,10-phenanthroline (DPA) and azole compounds For example 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (PBD) and 3- (4-biphenylyl) -4- Phenyl-5- (4-t-butylphenyl) -1,2,4-triazole (TAZ). Layer 4 serves to facilitate electron transport and acts as a buffer layer or barrier layer to prevent the exciton from quenching at the interface of the layer of the OLED. Layer 4 preferably improves the mobility of the electrons and reduces the quenching of the excitons.

Among the materials specified above as hole transport materials and electron transport materials, some may fulfill a plurality of functions. For example, some of the electron conducting materials become hole blocking materials at the same time when they have a low-lying HOMO.

The charge transport layer can also be used to improve the aqueous properties of the materials used, first to make the layer larger (avoidance of pinhole / short circuits), and secondly to minimize the operating voltage of the device. To be electronically doped. For example, the hole transport material may be doped with an electron acceptor, for example phthalocyanine or arylamine, such as TPD or TDTA, may be doped with tetrafluorotetracyanoquinodimethane (F4-TCNQ). . The electron transport material can be doped with, for example, an alkali metal, Alq ₃ -including lithium. Electronic doping is known to those skilled in the art, see, eg, W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, No. 1, July 1, 2003 (p-doped Organic layers); See AG Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No. 25, June 23, 2003 and Pfeiffer et al., Organic Electronics 2003, 4, 89-103.

The cathode 5 is an electrode which serves to introduce electrons or negative charge carriers. The cathode can be any metal or nonmetal having a lower work function than the anode. Suitable materials for the cathode are alkali metals of group Ia of the periodic table of the elements (formerly IUPAC version), for example, alkaline earth metals of groups Li, Cs, IIa, metals of group IIb, including rare earth metals and lanthanide elements and actinides. Selected from the group consisting of. In addition, metals such as aluminum, indium, calcium, barium, samarium and magnesium, and combinations thereof, may also be used. In addition, a lithium-containing organometallic compound or LiF may be applied between the organic layer and the cathode to reduce the operating voltage.

The OLED of the present invention may further comprise additional layers known to those skilled in the art. For example, a layer can be applied between layer 2 and the light emitting layer 3 to facilitate the transport of positive charges and / or to match the band gaps of the layers to each other. Alternatively, this additional layer may serve as a protective layer. In a similar manner, additional layers may be present between the light emitting layer 3 and the layer 4 to facilitate the transport of negative charges and / or to match the band gap between the layers to each other. Alternatively, this layer may serve as a protective layer.

In a preferred embodiment, the inventive OLED comprises at least one of the additional layers mentioned below in addition to the layers (1) to (5):

A hole injection layer between the anode 1 and the hole transport layer 2;

An electron blocking layer between the hole transport layer 2 and the light emitting layer 3;

A hole blocking layer between the light emitting layer 3 and the electron transport layer 4;

An electron injection layer between the electron transport layer 4 and the cathode 5.

However, it is also possible that the OLED does not have all of the specified layers (1) to (5), for example, layer (1) (anode), layer (3) (light emitting layer) and layer (5) (cathode) OLEDs having are likewise suitable, in which case the function of layer 2 (hole transport layer) and layer 4 (electron transport layer) is assumed by the adjacent layers. OLEDs with layers (1), (2), (3) and (5) or (1), (3), (4) and (5) are likewise suitable.

Those skilled in the art will know how to select a suitable material (eg based on electrochemical investigation). Suitable materials for the individual layers are known to those skilled in the art and are disclosed, for example, in WO 00/70655.

In addition, each of the specified layers of the OLED of the present invention may consist of two or more layers. In addition, some or all of the layers (1), (2), (3), (4) and (5) can be surface treated for an increase in the efficiency of charge carrier transport. The choice of material in each of the layers mentioned is preferably determined by obtaining a highly efficient OLED.

The OLED of the present invention can be manufactured by methods known to those skilled in the art. In general, the OLEDs of the present invention are produced by successive vapor deposition of individual layers onto a suitable substrate. Suitable substrates are, for example, glass or polymer films. In vapor deposition, conventional techniques such as thermal evaporation, chemical vapor deposition and other techniques may be used. In alternative processes, the organic layer from a solution or dispersion in a suitable solvent may be coated, in which case coating techniques known to those skilled in the art are used.

In general, the different layers have the following thicknesses: Anode (1): 500 to 5000 kPa; Preferably 1000 to 2000 mm 3; Hole transport layer (2): 50 to 1000 kPa, preferably 200 to 800 kPa; Light emitting layer (3): 10 to 1000 Hz, preferably 100 to 800 Hz; Electron transport layer (4): 50 to 1000 Hz, preferably 200 to 800 Hz; Cathode (5): 200 to 10 000 mm 3, preferably 300 to 5000 m 3. The location of the recombination band of holes and electrons in the OLED of the present invention, and therefore the emission spectrum of the OLED, may be affected by the relative thickness of each layer. This means that the thickness of the electron transporting layer should preferably be chosen so that the electron / hole recombination zone is present in the emissive layer. The ratio of the layer thicknesses of the individual layers in the OLED depends on the material used. The layer thickness of any additional layer is known to those skilled in the art.

In the light emitting layer of the OLED of the present invention, an OLED having high efficiency can be obtained by the use of phenoxazine, phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide derivative of the formula I used according to the present invention. Obtained. The efficiency of the OLED of the present invention may be further improved by optimization of other layers. For example, highly efficient cathodes such as Ca, Ba or LiF may be used. Novel hole transport materials and molded substrates that result in reduced operational response or increased quantum efficiency are likewise usable in the inventive OLED. In addition, additional layers may be present in the OLED to adjust the energy levels of the different layers and to facilitate field emission. In addition, phenoxazine derivatives, phenothiazine derivatives, phenothiazine S-oxides or phenothiazine S, S-dioxide derivatives of the formulas used according to the invention are suitable as hole and excitone blockers, And in an exciton-blocking layer.

The OLED of the present invention can be used in any device in which electric field emission is useful. Suitable devices are preferably selected from stationary and mobile visual display units (VDUs). Stationary VDUs include, for example, VDUs of computers, televisions, printers, kitchen appliances and advertising panels, and VDUs of lighting and information panels. Mobile VDUs are, for example, mobile phones, laptops, digital cameras, VDUs in vehicles and destination displays on buses and trains.

In addition, phenoxazine, phenothiazine, phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives of the formula (I) used according to the invention may also be used in OLEDs having an inverse structure. Preferred for such inverted OLEDs is the use of the compounds of the formula (I) used according to the invention in the emissive layer, more preferably in the emissive layer without further additives, or in the hole- and exciton-blocking layers. The structure of inverse OLEDs and the materials commonly used therein are known to those skilled in the art.

The present invention provides phenothiazine S, S-dioxide derivatives selected from the group consisting of compounds of the formulas XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI and XXII:

[In the formula,

R ¹ , R ¹² are each H, Me, Et or unsubstituted phenyl;

R ^{1 '} is 4-methoxyphenyl or mesityl;

R ⁶ is Me or unsubstituted phenyl;

R ¹⁷ is methoxy;

s is 0 or 2, wherein when s is 2 the substituents are preferably arranged in 2- and 5-positions;

Ph is unsubstituted phenyl;

Naphthyl is 1- or 2-naphthyl;

R ²⁸ is H or -CHO]

, And

Phenothiazine derivatives selected from the group consisting of compounds of formulas XXIII, XXIV, XXV, XXVI, XXVII, XXVIII and XXIX:

[In the formula,

R ¹ , R ¹² are each H, Me, Et or unsubstituted phenyl;

Ph is unsubstituted phenyl;

Naphthyl is 1- or 2-naphthyl;

임] R ²⁹ , R ³⁰ are each -CHO or

being]

, And

Phenothiazine S-oxide derivative of formula

[In the formula,

R ¹ is H, Me, Et or unsubstituted phenyl;

Naphthyl is 1- or 2-naphthyl]

Also provides.

The present invention provides phenothiazine S, S-dioxide derivatives selected from the group consisting of compounds of the formulas XXXI and XXXII:

[In the formula,

R ¹ is phenyl or pyridyl substituted with one OH, OC (O) Ph, OCH ₂ Ph or N-phenylbenzimidazolyl group, three CH ₃ groups or two F radicals; Preferably 2-hydroxyphenyl, 4-hydroxy-phenyl, 2-benzoyloxyphenyl, 4-benzoyloxyphenyl, 4-benzyl-oxyphenyl, 3,5-difluorophenyl, mesitylenyl, 4 -(2'-N-phenyl-benzimidazolyl) phenyl, 4-methoxyphenyl, 2-thienyl, 2-pyridyl,

R ³ is H or CHO, preferably H,

R ¹² is phenyl substituted with three CH ₃ groups, preferably mesitylenyl]

And phenothiazine derivatives of Formula XXXIII:

[In the formula,

R ¹ is phenyl or pyridyl substituted with one OH, OC (O) Ph, OCH ₂ Ph or N-phenylbenzimidazolyl group, three CH ₃ groups or two F radicals; Preferably 2-hydroxyphenyl, 4-hydroxy-phenyl, 2-benzoyloxyphenyl, 4-benzoyloxyphenyl, 3,5-difluorophenyl, mesitylenyl, 4- (2'-N- Phenyl-benzimidazolyl) phenyl, 4-methoxyphenyl, 2-thienyl, 2-pyridyl,

R ³ is H or CHO, preferably H]

Also provides.

Phenothiazine S, S-dioxide derivatives of the aforementioned formulas XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI and XXII and XXXI, XXXII, and the formulas XXIII, XXIV, XXV, XXVI, XXVII, XXVIII and Phenothiazine derivatives of XXIX and XXXIII and phenothiazine S-oxide derivatives of Formula (XXX) are particularly suitable for use in OLEDs, phenothiazine S, S-oxide derivatives of Formula (XXII) and phenoti of Formula (XXIX) The azine derivatives are particularly suitable as intermediates for the preparation of the phenothiazine S, S-dioxide and phenothiazine derivatives of the present invention. Compounds of the invention of formulas XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII, XXIX and XXX and XXXI, XXXII and XXXIII are blue in the electromagnetic spectrum It is particularly suitable as the charge transport material or emitter material to emit light in the region. Phenothiazine-S, S-dioxide derivatives of formulas XIV, XVII, XIX, XXI, XXII, XXIII, XXVI, XXVIII, XXIX, preferably XIV, XXI, XXII, XXIII, XXVII, XXIX and XXXI and XXXIII and Phenothiazine derivatives are particularly suitable as emitter blockers or hole blockers. In addition, compounds of the formulas XV, XVI, XXIII, XXIV, XXV, XXVI, XXVII and XXVIII can be used as matrix material. Preference is given to using the compounds of the invention in the light emitting layer of the OLED as emitter materials which preferably emit light in the blue region of the electromagnetic spectrum or as hole and exciton blockers. Very particular preference is given to using them as emitter materials in the light emitting layer of the OLED or in the hole- and exciton-blocking layers.

Accordingly, the present application also provides the use of the phenothiazine S, S-dioxide derivatives of the present invention and phenothiazine derivatives of the present invention in OLEDs, and OLEDs comprising at least one of the compounds of the present invention. Preferred embodiments of suitable OLEDs and of individual layers of OLEDs and of suitable materials for the cathode and anode are specified above.

It is preferable to use the compound of the present invention in the light emitting layer in the light emitting layer. Accordingly, the present application also provides a light emitting layer comprising at least one phenothiazine S, S-dioxide derivative or phenothiazine derivative of the present invention. The present application also provides an OLED comprising the light emitting layer of the present invention. In a further preferred embodiment, the compounds of the invention are used in hole- and excitone-blocking layers. Accordingly, the present invention also provides an hole- and exciton-blocking layer comprising at least one compound of the present invention and an OLED comprising the hole and exciton-blocking layer of the present invention. Suitable OLEDs and individual layers of OLEDs and suitable materials for anodes and cathodes are specified above. Depending on the substitution pattern of the compound of the present invention, the compound of the present invention may satisfy different functions in the light emitting layer or in the hole- and exciton-blocking layer. Preference is given to using the compounds of the invention as emitter materials.

Phenothiazine S, S-dioxide derivatives of the present invention of Formulas XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI and XXII and XXXI and XXXII, and Formulas XXIII, XXIV, XXV, XXVI, XXVII, XXVIII And phenothiazine derivatives of XXIX and XXXIII, and phenothiazine S-oxide derivatives of Formula (XXX) can be prepared by the methods specified above. Phenothiazine S, S-dioxide derivatives of the invention of Formulas XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI and XXII, and Formulas XXIII, XXIV, XXV, XXVI, XXVII, XXVIII and XXIX and XXXIII The phenothiazine derivatives of the present invention and corresponding methods of preparing phenothiazine S-oxide derivatives of the formula XXX also likewise form part of the technical content of the present application.

The following examples further illustrate the invention.

Example  1: 3- Phenylphenothiazine  5,5- Dioxide

2.00 g (7.2 mmol) of 3-phenylphenothiazine in 45 ml of methylene chloride (J. Cymerman-Craig, WP Rogers and GP Warwick, Aust. J. Chem. 1955, 8, 252-257) The suspension was mixed in portions with 3.40 g (13.8 mmol) of 70% m-chloroperbenzoic acid while stirring at room temperature. After stirring for 4 hours at room temperature, the precipitate was filtered off, washed with methylene chloride and dried under reduced pressure. The crude product (0.95 g) was recrystallized twice from acetic acid. After drying the light gray solid at 100 ° C. under high vacuum, 0.492 g (22% theoretical) of analytical pure material having a melting point of 269-272 ° C. were obtained, the solution of which was in tetrahydrofuran at λ = 383 nm. Fluorescence was performed.

Example  2: 10- methyl -3,7- Diphenylphenothiazine

2.50 g (6.7 mmol) of 3,7-dibromo-10-methylphenothiazine (C. Bodea and M.'Terdic, Acad. Rep. Rom. 1962, 13, 81-87), 1.85 g (14.9 mmol) of 98% phenylboric acid, 0.11 g (0.14 mmol) of bis (triphenylphosphine) palladium dichloride and 1.03 g (7.4 mmol) of potassium carbonate in 55 ml of dimethoxyethane and 28 ml of water Heated and boiled (75 ° C.) for 5 hours under reflux under nitrogen. The reaction mixture was cooled to room temperature and further stirred overnight. The precipitate was filtered off with suction, washed successively with 125 ml of ethanol and hot water and dried at 70 ° C. under reduced pressure. The crude product (2.30 g) was heated to boil for 2 hours under reflux in cyclohexane. After the hot suspension was filtered, the residue was dried, dissolved in 40 ml of methylene chloride and filtered through a silica-gel-filled glass frit. After removal of the solvent, 1.05 g (43% theoretical) of a pale yellow analytical pure solid having a melting point of 239-241 ° C., the solution in chloroform fluoresced at λ = 464 nm.

Example  3: 10- methyl -3,7- Diphenylphenothiazine  5,5- Dioxide

A solution of 1.95 g (5.3 mmol) of 10-methyl-3,7-diphenylphenothiazine in 65 mL ml of methylene chloride was mixed with 2.67 g (10.7 mmol) of 70% m-chloroperbenzoic acid in portions at room temperature. Stir at 20-25 ° C. for 2 hours. The reaction solution was then extracted successively twice in each case with 10 ml of 10% potassium hydroxide solution, 10 ml of 5% hydrochloric acid and 10 ml of saturated sodium bicarbonate solution. The organic phase was transferred and purified by column chromatography (eluant: ethyl acetate). The resulting crude product (1.80 g) was recrystallized from toluene and then sublimed under high vacuum. 0.65 g (31% theory) of a light beige analytical pure solid having a melting point of 242-245 ° C. were obtained and the solution in chloroform fluoresced at λ = 386 nm.

Example  4: 10- methyl -3,7- Bis (1-naphthyl) phenothiazine

9.30 g (25.1 mmol) 3,7-dibromo-10-methylphenothiazine, 9.50 g (55.2 mmol) 1-naphthylboric acid, 0.407 g (0.50 mmol) bis (triphenylphosphane)- Palladium dichloride and 3.80 g (27.5 mmol) of potassium carbonate were heated and boiled under reflux under nitrogen in 204 ml of dimethoxyethane and 101 ml of water for 5 hours. The reaction mixture was cooled to rt, further stirred overnight and then filtered. The residue was washed with 470 ml of ethanol and hot water and dried at 70 ° C. under reduced pressure. The solid was dissolved in 100 ml methylene chloride and filtered through silica gel. After the solvent was removed under reduced pressure, a cohesive mass was obtained, which crystallized with stirring after adding 200 ml of methanol. The crystals were filtered off with suction, washed with 300 ml of methanol and dried at 40 ° C. under reduced pressure. 10.33 g of pale yellow fine crystals having a melting point of 185-190 ° C were obtained. The crude product was recrystallized twice from ethyl acetate. 5.71 g (49% theory) of analytical pure, nearly colorless microcrystals having a melting point of 191-194 ° C. were obtained, and the solution in chloroform fluoresced at λ = 468 nm.

Example  5: 10- methyl -3,7- Bis (1-naphthyl) phenothiazine  5- Oxid

A solution of 1.20 g (5.35 mmol) of 77% m-chloroperbenzoic acid in 20 ml methylene chloride was added 2.50 g (5.37 mmol) of 10-methyl-3,7-bis (1-naphthyl) in 60 ml methylene chloride ) Was added dropwise to the ice cold suspension of phenothiazine within 30 minutes. The reaction solution was stirred at 0-5 ° C. for 2 hours. Thereafter, an additional 0.60 g (2.70 mmol) of m-chloroperbenzoic acid dissolved in 10 ml of methylene chloride was added dropwise. This solution was stirred for an additional 2 hours at 0-5 ° C. and then warmed to room temperature. The reaction solution was extracted twice in each case with 15 ml of 10% KOH, 15 ml of 5% HCl and 25 ml of saturated sodium bicarbonate solution, and then the organic phase was purified by column chromatography on silica gel (eluant: methylene chloride). Purified. The first fraction contained sulfone (see Example 6) from which 0.38 g (14% theoretical) of analytical pure colorless solid having a melting point of 221-225 ° C. was isolated, the solution of which was in chloroform at λ = 385 μm Fluorescence was performed. After removing the sulfone, the eluent was changed to ethyl acetate. After the solvent was removed, a tacky paste was obtained, which crystallized after the addition of water. 1.53 g (59% theory) of 10-methyl-3,7-bis (1-naphthyl) phenothiazine S-oxide was obtained as an analytical pure light brown solid having a decomposition point> 150 ° C., and its chloroform The heavy solution fluoresced at λ = 388 nm. 10-Methyl-3,7-bis (1-naphthyl) -phenothiazine 5,5-dioxide was obtained as a byproduct.

Example  6: 10- methyl -3,7- Bis (1-naphthyl) phenothiazine  5,5- Dioxide

See under Example 5 for the preparation as a by-product in the synthesis of 10-methyl-3,7-bis (1-naphthyl) phenothiazine 5-oxide. At least 2 molar equivalents of m-chloroperbenzoic acid are used for the selective preparation of sulfones. Colorless microcrystals having a melting point of 221-225 ° C. were obtained, and the solution in chloroform fluoresced at λ = 385 nm.

Example  7: 10- methyl -3,7- Bis (2-naphthyl) phenothiazine

9.30 g (25.1 mmol) 3,7-dibromo-10-methylphenothiazine, 9.50 g (55.2 mmol) 2-naphthylboric acid, 0.407 g (0.50 mmol) bis (triphenylphosphine)- Palladium dichloride and 3.80 g (27.5 mmol) of potassium carbonate were heated and boiled under reflux under nitrogen in 204 ml of dimethoxyethane and 101 ml of water for 5 hours. The reaction mixture was cooled to room temperature, further stirred overnight, and then filtered. The residue was washed with 470 ml of ethanol and hot water and then dried at 70 ° C. under reduced pressure. The solid was dissolved in 200 ml of methylene chloride and filtered through silica gel. After removal of the solvent under reduced pressure, a greenish yellow 9.6 g solid was obtained (melting point: 276-281 ° C.) and recrystallized from 500 ml of toluene. 7.10 g (81% theory) of analytical pure, shiny yellow microcrystals having a melting point of 285-289 ° C. were obtained and the solution in chloroform fluoresced at λ = 402 μm nm.

Example  8: 10- methyl -3,7- Bis (2-naphthyl) phenothiazine  5- Oxid

A solution of 1.20 g (5.35 mmol) of 77% m-chloroperbenzoic acid in 20 ml methylene chloride was added 2.50 g (5.37 mmol) of 10-methyl-3,7-bis (2-naphthyl) in 60 ml methylene chloride. ) Was added dropwise to the ice cold suspension of phenothiazine within 30 minutes. The reaction mixture was stirred at 0-5 ° C. for 2 hours. Thereafter, an additional 0.60 g (2.70 mmol) of m-chloroperbenzoic acid dissolved in 10 ml of methylene chloride was added dropwise. The solution was further stirred at 0-5 ° C. for 2 hours, then warmed to room temperature. The reaction mixture is extracted twice in each case with 15 ml of 10% KOH, 15 ml of 5% HCl and 25 ml of saturated sodium bicarbonate solution, and then the organic phase is purified by column chromatography on silica gel (eluant: methylene chloride). Purified. The first fraction contained 0.62 g of sulfone (see Example 9), which was recrystallized from 36 ml of o-dichlorobenzene. A yellowish solid having 0.44 g (16% theoretical) having a melting point of 328-332 ° C was obtained. After removing the sulfone, the eluent was changed to ethyl acetate. After removal of the solvent, 1.30 g of solid was obtained and recrystallized from 134 ml of acetic acid. 0.54 g (21% theory) of 10-methyl-3,7-bis (2-naphthyl) phenothiazine 5-oxide was obtained as an analytical pure beige solid having a melting point of 275-280 ° C. and its chloroform The heavy solution fluoresced at λ = 402 nm. 10-Methyl-3,7-bis (2-naphthyl) phenothiazine 5,5-dioxide was obtained as a byproduct.

Example  9: 10- methyl -3,7- Bis (2-naphthyl) phenothiazine  5,5- Dioxide

See Example 8 for the preparation as a by-product in the synthesis of 10-methyl-3,7-bis (2-naphthyl) phenothiazine 5-oxide. At least 2 molar equivalents of m-chloroperbenzoic acid are used for the selective preparation of sulfones. Yellowish fine crystals having a melting point of 328-332 ° C were obtained.

Example  10: 10- methyl -3,7- Bis (2-phenylpropenyl) phenothiazine

3.46 g (30.4 mmol) potassium tert-butoxide followed by 3.60 g (13.4 mmol) of 10-methylphenothiazine-3,7-dicarbaldehyde (see H. Oelschlager and HJ Peters, Arch. Pharm. Weinheim) 320, 379-381, 1987)) 6.50 g (26.8 mmol) of diethyl (1-phenylethyl) phosphonate (Example 13 in US 5,130,603) in 60 ml of anhydrous dimethyl sulfoxide with stirring at room temperature Was added to the solution, and the temperature was raised from 25 deg. C to 41 deg. After stirring for 5 hours at room temperature, the reaction solution was mixed with 150 ml of methanol, stirred for 15 minutes and filtered through a black band filter. The residue was washed with 300 ml of methanol and dried at 80 ° C. under reduced pressure. The crude product (3.6 g) was dissolved in 100 ml of methylene chloride, purified on silica gel and recrystallized from 480 ml of acetonitrile. 1.79 g (30% theory) of analytical pure, luminous yellow microcrystals having a melting point of 189-191 ° C. were obtained, and the solution in chloroform fluoresced at λ = 479 μm.

Example  11: 10- methyl -3,7- Bis (2-phenylpropenyl) phenothiazine  5,5- Dioxide

A solution of 1.70 g (3.81 mmol) of 10-methyl-3,7-bis (2-phenylpropenyl) phenothiazine in 65 ml of methylene chloride was diluted with 1.90 (g (7.60 mmol) of m-chloroperbenzoic acid at room temperature. Mix portionwise and stir for a further 2 hours. The reaction solution was extracted twice in each case with 10 μl of 10% KOH, 10 ml of 5% HCl and 10 ml of saturated sodium bicarbonate solution. The organic phase was diluted to 100 ml with methylene chloride and then purified on silica gel, in which the eluent was changed to ethyl acetate. This purified solid (1.00 g) was recrystallized from 40 ml of ethyl acetate. 0.57 g (31% theory) of analytical pure colorless microcrystals having a melting point of 190-193 ° C. were obtained and the solution in chloroform fluoresced at λ = 394 nm.

Example  12: 3,7- Vis (2,2- Diphenylvinyl ) -10- Methylphenothiazine

3.46 g (30.4 mmol) of potassium tert-butoxide followed by 3.60 g (13.4 mmol) of 10-methylphenothiazine-3,7-dicarbaldehyde with 8.20 in 60 ml of anhydrous dimethyl sulfoxide at room temperature with stirring g (26.8 mmol) to a solution of diethyl benzhydrylphosphonate (prepared similar to Example 13 of US 5,130,603), in which the temperature was raised from 25 ° C to 43 ° C. After stirring for 5 hours at room temperature, the reaction solution was mixed with 150 ml of methanol, stirred for 15 minutes and filtered through a black band filter. The residue was washed with 300 ml of methanol and dried at 80 ° C. under reduced pressure. The crude product (4.7 g) was dissolved in 150 ml of methylene chloride, purified on silica gel and recrystallized from 83 ml of butylglycol. 3.56 g (23% theory) of greenish fine crystals having a melting point of 233-241 ° C were obtained.

Example  13: 3,7- Vis (2,2- Diphenylvinyl ) -10- Methylphenothiazine  5,5- Dioxide

A solution of 1.80 g (3.16 mmol) of 10-methyl-3,7-bis (2-phenylpropenyl) phenothiazine in 65 ml of methylene chloride was added at 1.60 g (6.5 mmol) of 70% m-chloroper at room temperature. Partially mixed with benzoic acid and stirred for a further 2 hours. The reaction solution was extracted twice in each case with 10 μl of 10% KOH, 10 ml of 5% HCl and 10 ml of saturated sodium bicarbonate solution. After removing the solvent, the solid (1.20 g) was recrystallized from 184 ml of acetic acid. 0.86 g (45% theory) of analytical pure, almost colorless microcrystals having a melting point of 246-252 ° C. were obtained, which dissolved in chloroform fluoresced at λ = 453 nm.

Example 14: 3,7- Vis [1,3- Vis ( Trifluoroacetyl ) -2,3- Dihydroimidazole -2-yl] -10- Phenylphenothiazine

228.8 g (1.09 mol) trifluoroacetic anhydride was added dropwise to a solution of 28.2 g (0.416 mol) imidazole in 396 ml anhydrous acetonitrile within 5 minutes under nitrogen with stirring. After heating this solution to reflux, 55.0 g (0.198 mol) of 10-phenylphenothiazine (J. Cymerman-Craig, WP Rogers and GP Warwick, Aust. J. Chem. 1955, 8, 252- 257]). This solution was heated to boiling under reflux for 8 hours. The solvent is then distilled off and the residue is mixed with ice / water and sodium carbonate. The solid was filtered off with suction and suspended in 825 ml of methanol. This suspension was aspirated through a suction filter and the residue was washed twice with 50 ml of ether each time and dried under reduced pressure. 110 μg of yellowish solid was obtained.

Example  15: 10- Phenylphenothiazine -3,7- Dicarbaldehyde

14.0 g (17.6 mmol) of 3,7-bis [1,3-bis (trifluoroacetyl) -2,3-dihydroimidazol-2-yl] -10-phenylphenono in 350 ml of acetonitrile The solution of azine was heated and boiled under reflux for 3 hours after the addition of 200 ml of 1.9 N HCl. After cooling to room temperature, the suspension was filtered. After the filtrate was concentrated, the formed precipitate was filtered off with suction, washed with water until neutral and dried at 80 ° C. under reduced pressure (3.0 g of dark yellow solid). This solid was dissolved in 25 ml of methylene chloride and purified on silica gel. 1.29 g of an orange solid having a melting point of 194-198 ° C. were obtained.

Example  16: 3,7- Vis (2,2- Diphenylvinyl ) -10- Phenylphenothiazine

6.63 g (58.1 mmol) potassium tert-butoxide, followed by 8.50 g (25.7 mmol) of 10-phenylphenothiazine-3,7-dicarbaldehyde in 121 ml of dimethyl sulfoxide dried over molecular sieves To a solution of 15.61 g (51.3 mmol) of diethyl benzhydrylphosphonate (prepared similar to Example 13 of US 5,130,603) was added with stirring at room temperature. After stirring for 5 hours at room temperature, the reaction solution was diluted with 1500 ml of methanol and stirred for an additional 15 minutes. The precipitate was filtered off, washed with methanol and dried at 80 ° C. under reduced pressure. 6.92 g (43% theoretical) of a yellowish solid having a melting point of 232-237 ° C were obtained.

Example  17: 3,7- Vis (2,2- Diphenylvinyl ) -10- Phenylphenothiazine  5,5- Dioxide

A solution of 6.85 g (10.8 mmol) of 3,7-bis (2,2-diphenylvinyl) -10-phenylphenothiazine in 250 ml of methylene chloride was prepared at 5.84 g (26.1 mmol) of 77% m- at room temperature. The mixture was partially mixed with chloroperbenzoic acid and stirred for a further 2 hours. The reaction solution was extracted in each case with 30 μl 10% KOH, 30 ml 5% HCl and 30 ml saturated sodium hydrogen carbonate solution. After the solvent was removed, the solid (7.19 g) was dissolved in 40 ml of methylene chloride and purified on silica gel. After removal of the solvent, 4.86 g (65% theory) of analytical pure yellowish microcrystals having a melting point of 269-274 ° C. were obtained and the solution in methylene chloride fluoresced at λ = 454 nm.

Example  18: 10- methyl -3- (2- {4 '-[2- (10- Methylphenothiazine -3-yl) vinyl] biphenyl-4-yl} vinyl) phenothiazine

0.80 g (7.1 mmol) of potassium tert-butoxide, followed by 1.82 g (3.3 mmol) of 10-methylphenothiazine-3-carbaldehyde, is 1.42 g in 32 ml of dimethyl sulfoxide dried over molecular sieves ( 3.14 mmol) in a solution of diethyl [4 '-(diethoxyphosphoryl-methyl) biphenyl-4-ylmethyl] phosphonate (US 3,984,399, Example 2, stage 29, lines 58-66) under nitrogen Add with stirring at room temperature. After stirring for 4 hours at room temperature, the reaction solution was diluted with 70 ml of methanol and stirred for an additional 15 minutes. The precipitate was filtered off, washed with 172 ml of methanol and dried at 35 ° C. under reduced pressure. The crude product (1.70 g) was recrystallized in 255 ml of N-methylpyrrolidone. After removal of the solvent residue at 225 ° C. under high vacuum, 0.98 g (50% theoretical) of analytical pure yellow solid having a melting point of 380 ° C. was obtained, the solution of which in N-methylpyrrolidone was at λ = 576 nm. Fluorescence was performed.

Example 19: 10- methyl -3- (2- {4 '-[2- (10- methyl -5,5- Dioxofenothiazine -3-yl) -vinyl] biphenyl-4-yl} vinyl) phenothiazine 5,5- Dioxide

1.02 g (9.05 mmol) of potassium tert-butoxide followed by 2.20 g (8.05 mmol) of 10-methyl-5,5-dioxophenothiazine-3-carbaldehyde (Example 21) molecular sieve To a solution of 1.82 g (4.00 mmol) of diethyl [4 '-(diethoxyphosphorylmethyl) biphenyl-4-ylmethyl] phosphonate in 41 ml of dimethyl sulfoxide was added with stirring at room temperature under nitrogen. After stirring for 4 hours at room temperature, the reaction solution was diluted with 90 ml of methanol and stirred for an additional 15 minutes. The precipitate was filtered off, washed with 220 ml of methanol and dried at 35 ° C. under reduced pressure. The crude product (2.50 g) was recrystallized in 58 ml of dimethyl sulfoxide. After removal of the solvent residue at 200 ° C. under high vacuum, 1.64 g (59% theory) of analytical pure yellow solid having a melting point of 360 ° C. were obtained, the solution of which was in N-methylpyrrolidone at λ = 460 nm. Fluorescence was performed.

Example  20: 10- Phenyl -3- (2- {4 '-[2- (10- Phenylphenothiazine -3-yl) vinyl] biphenyl-4-yl} vinyl) phenothiazine

2.73 g (24.1 mmol) of potassium tert-butoxide, followed by 7.80 g (25.7 mmol) of 10-phenylphenothiazine-3-carbaldehyde, 4.83 g (in 80 ml of dimethyl sulfoxide dried on a molecular sieve) 10.7 mmol) was added to a solution of diethyl [4 '-(diethoxyphosphorylmethyl) biphenyl-4-ylmethyl] phosphonate with stirring at room temperature under nitrogen. After stirring for 4 hours at room temperature, the reaction solution was diluted with 200 ml of methanol and stirred for an additional 15 minutes. The precipitate was filtered off, washed with 500 ml of methanol and dried at 35 ° C. under reduced pressure. The crude product (5.85 g) was recrystallized in 400 ml of toluene. 3.85 g of a yellow solid having a melting point of 278-290 ° C. were obtained.

Example  21: 10- Phenyl -5,5- Dioxofenothiazine -3- Carbaldehyde

A solution of 1.01 g (3.33 mmol) of 10-phenylphenothiazine-3-carbaldehyde in 35 mL ml of methylene chloride was mixed in portions with 1.48 g (6.6 mmol) of 77% m-chloroperbenzoic acid at room temperature and added Stirred for 2 hours. The reaction solution was extracted twice in each case with 10 ml 10% KOH, 10 ml 5% HCl and 10 ml saturated sodium bicarbonate solution. After the solvent was removed, the solid (0.87 g) was dissolved in a mixture of 19.6 ml of methylene chloride and 0.4 ml of methanol and purified on silica gel. After the solvent was removed, 0.395 g of yellowish fine crystals having a melting point of 260-272 ° C. were obtained.

Example  22: 10-phenyl-3- (2- {4 '-[2- (10-phenyl-5,5-dioxophenothiazin-3-yl) vinyl] -biphenyl-4-yl} vinyl) phenyl Notthiazine 5,5- Dioxide

2.28 g (19.9 mmol) of potassium tert-butoxide followed by 5.90 g (17.6 mmol) of 10-phenyl-5,5-dioxophenothiazine-3-carbaldehyde (Example 21) To a solution of 4.00 g (8.80 mmol) of diethyl [4 '-(diethoxyphosphorylmethyl) biphenyl-4-ylmethyl] -phosphonate in dried 45 ml of dimethyl sulfoxide while stirring at room temperature under nitrogen Added. After 72 hours of stirring at room temperature, the reaction solution was diluted with 200 ml of methanol and stirred for a further 1 hour. The precipitate was filtered off, washed with 500 ml of methanol and dried at 80 ° C. under reduced pressure. The crude product (5.44 g) was recrystallized in 250 ml o-dichlorobenzene. The crystals were filtered off with suction, washed successively with o-dichlorobenzene and ethanol, filtered off with suction and dried at 80 ° C. under reduced pressure. After removing the solvent residue at 250 ° C. under high vacuum (2 × 10 ⁻⁵ mbar), 4.35 g (60% theoretical) of yellow microcrystals having a melting point of 392 ° C. were obtained, the solution of which was in ethylene = 456 Fluorescence at nm.

Example  23: 1,3- Phenylene -10,10'- Vis (Phenothiazine)

This preparation is described in K. Okada et al., J. Am. Chem. Soc. 1996, 118, 3047-3048.

18.5 g (91.9 mmol) phenothiazine, 15.6 g (46.3 mmol) 98% 1,3-diiodobenzene, 19.4 g (140 mmol) potassium carbonate and 1.16 g (18.3 mmol) activated copper powder Heated to 200 ° C. and stirred at this temperature for 24 hours. The reaction mixture was cooled to 140 ° C. and then mixed with 200 mL ml of ethyl acetate. This suspension was heated to reflux for 1 hour under reflux and then hot filtered. The filtrate was diluted with 300 ml of methanol, the solid precipitated out and filtered off with suction, washed with methanol and dried at 80 ° C. under reduced pressure. 8.91 g of a pink solid having a melting point of 186-188 ° C. were obtained.

Example  24: 1,3- Phenylene -10,10'-bis (phenothiazine 5,5- Dioxide )

6.28 g (13.3 mmol) of 1,3-phenylene-10,10'-bis (phenothiazine) were dissolved in 220 ml of methylene chloride. After stirring for 15 minutes at room temperature, 17.9 g (79.9 mmol) of 77% m-chloroperbenzoic acid was added in portions. The reaction solution was stirred at room temperature for 24 hours during which time a solid precipitated out. This solution was filtered and the residue was washed with methylene chloride and suction dried. The solid was suspended in hot water. The aqueous suspension was adjusted to pH 11 with 5% potassium hydroxide solution and then hot filtered. The residue was washed with hot water and dried at 80 ° C. under reduced pressure. Solid (5.07 g) was recrystallized from dimethylformamide. 3.72 g of colorless microcrystals having a melting point of 412 ° C. were obtained in an analytically pure form, the solution in toluene fluorescing at λ = 375 nm (S).

Example  25: 1,4- Phenylene -10,10'-bis (phenothiazine 5,5- Dioxide )

a) 1,4- Phenylene -10,10'- Vis (Phenothiazine)

This preparation is described in K. Okada et al., J. Am. Chem. Soc. 1996, 118, 3047-3048.

19.9 g (98.9 mmol) phenothiazine, 16.6 g (49.8 mmol) 99% 1,4-diiobenzene, 20.9 g (151 mmol) potassium carbonate and 1.25 g (19.7 mmol) activated copper powder Heated to 196 ° C. and stirred at this temperature for 17 hours. After the reaction mixture was cooled to room temperature, 200 ml of hot water was added. This suspension was stirred for 1 hour and then filtered. The residue was washed with hot water and dried at 80 ° C. under reduced pressure. The crude product was heated to boil for 1 hour under reflux in 200 μml of methylene chloride. After cooling this solution to room temperature, it was filtered through silica gel. Three fractions were obtained, the first two of which were combined (11.7 g) and recrystallized from ethyl acetate. The third fraction contains the desired valuable product (5.0 g). In total, 13.47 g of beige solid having a melting point of 254-263 ° C were obtained.

b) 1,4- Phenylene -10,10'-bis (phenothiazine 5,5- Dioxide )

4.98 g (10.5 mmol) of 1,4-phenylene-10,10'-bis (phenothiazine) was dissolved in 175 ml of methylene chloride. After 1 hour of stirring at room temperature, 10.41 g (46.5 mmol) of 77% m-chloroperbenzoic acid was added in portions. The reaction solution was stirred at room temperature for 24 hours during which time a solid precipitated out. This solution was filtered and the residue was washed with methylene chloride and suction dried. The solid was suspended in 200 ml of hot water. The aqueous suspension was adjusted to pH 11.3 with 5 ml of 10% potassium hydroxide solution, stirred for 1 hour, and then hot filtered. The residue was washed with hot water and dried at 80 ° C. under reduced pressure. The residue (5.37 g) was recrystallized twice from sulfolane. 2.87 g (51%) of pale pink microcrystals having a melting point> 360 ° C. were obtained in analytical pure form, the solution of which in methylene chloride fluoresced at λ = 480 nm.

Example  26: 10- Methylphenothiazine  5,5- Dioxide

This preparation is described in M. Tosa et al., Heterocyclic Commun. 7 (2001) 277-282.

A solution of 10.0 g (45.9 mmol) of 98% 10-methylphenothiazine in 350 ml methylene chloride was mixed with 22.65 g (91.9 mmol) of 70% m-chloroperbenzoic acid at room temperature for 5 hours at 20-25 ° C. Was stirred. After the solution was filtered, the filtrate was extracted twice in each case with 100 ml of 10% potassium hydroxide solution, successively 100 ml of 5% hydrochloric acid and 70 ml of saturated sodium hydrogen carbonate. The organic phase was concentrated to 150 ml and then filtered through silica gel. From the second fraction, 4.89 g (43% theoretical) of beige microcrystals having a melting point of 226-235 ° C. (lit. 225-226 ° C.) were isolated in analytical pure form. Recrystallization in acetic acid gave colorless crystals, which melted at 226-233 ° C. The solution of this material in chloroform fluoresces at λ = 351, 376 (S) nm.

Example  27: 10- Phenylphenothiazine  5,5- Dioxide

a) 10- Phenylphenothiazine

This preparation is described in D. Li et al., Dyes and Pigments 49 (2001) 181-186.

96.0 g (482 mmol) phenothiazine, 298.5 g (1434 mmol) 98% iodobenzene, 80.0 g (579 mmol) potassium carbonate and 2.00 g (31.5 mmol) copper powder heated to 190-200 ° C And stirred at this temperature for 6 hours. Thereafter, excess iodobenzene was distilled off. The reaction mixture was diluted with 480 ml of ethanol and heated to boiling for 1 hour under reflux. This solution was filtered hot. After cooling, the precipitate was filtered off with suction, washed with ethanol and dried under reduced pressure. 77.7 g (58.5% of theory) of gray microcrystals having a melting point of 95-96 ° C. (lit. 95-97 ° C.) were obtained.

b) 10- Phenylphenothiazine  5,5- Dioxide

H. Gilman and R.O. Ranck, J. Org. Chem. 1958, 23, 1903-1906, see compounds described in M. Tosa et al., Heterocyclic Commun. 7 (2001) 277-282.

5.50 g (20.0 mmol) of 10-phenylphenothiazine in 220 ml of methylene chloride was mixed with 11.84 g (48.0 mmol) of 70% m-chloroperbenzoic acid at room temperature and stirred at 20-25 ° C. for 8 hours. . This solution was concentrated to dryness. The residue was suspended in hot water and heated to 80-85 ° C. At this temperature, the pH was adjusted to 7-8 with 32 ml of 10% potassium hydroxide solution. The solution was stirred for an additional 30 minutes, then filtered, washed with hot water and dried at 80 ° C. under reduced pressure. The crude product (5.77 g) was dissolved in 30 ml of methylene chloride and filtered through silica gel. From the second fraction, 2.92 g (47% theoretical) of beige microcrystals having a melting point of 212-217 ° C. (lit. 212-213 ° C.) were isolated in analytical pure form. Recrystallization in acetic acid gave colorless crystals, which melted at 212-217 ° C. The solution of this material in chloroform fluoresces at λ = 348, 386 (S), 452 (S) nm.

Example  28: 10- (4- Methoxyphenyl Phenothiazine 5,5- Dioxide

a) 10- (4- Methoxyphenyl Phenothiazine

18.77 g (94.2 mmol) phenothiazine, 66.5 g (284 mmol) 98% 4-iodoanisole, 15.7 g (114 mmol) potassium carbonate and 0.392 g (6.17 mmol) copper powder were 190-200 Heated to C and stirred at this temperature for 48 hours. Thereafter, excess iodobenzene was distilled off. The reaction mixture was mixed with 200 ml of hot water and heated at 90 ° C. for 1 hour. This solution was filtered hot. After cooling, the precipitate was filtered off with suction, washed with ethanol and dried under reduced pressure. The crude product (29.0 g) was recrystallized from 345 ml of acetic acid. Beige microcrystals having 22.54 g (78.4% in theory) having a melting point of 173-176 ° C (lit. 172-174 ° C (ER Biehl et al., J. Heterocyclic Chem. 12 (1975) 397-399)) Obtained.

b) 10- (4- Methoxyphenyl Phenothiazine 5,5- Dioxide

A solution of 5.00 g (16.4 mmol) of 10- (methoxyphenyl) phenothiazine in 175 mL ml of methylene chloride is mixed with 9.76 g (39.6 mmol) of 70% m-chloroperbenzoic acid at room temperature and 20-25 ° C. Stirred for 4 h. This solution was concentrated to dryness. The residue was triturated in 200 ml of hot water and dried to 80-85 ° C. At this temperature, the pH was adjusted to 7-8 using 25 ml of 10% potassium hydroxide solution. The solution was stirred for an additional 30 minutes, then filtered, washed with hot water and dried at 80 ° C. under reduced pressure. The crude product (5.25 g) was dissolved in 70 ml of methylene chloride and filtered through silica gel. After removal of the solvent, 4.41 g (80% of theory) of colorless microcrystals having a melting point of 265-266 ° C. were isolated in analytical pure form. Recrystallization in acetic acid gave colorless crystals, which melted at 264-270 ° C. A solution of this material in chloroform fluoresces at λ = 474 nm.

Example  29: 10- Mesitylphenothiazine  5,5- Dioxide

a) 10- Mesitylphenothiazine

9.92 g (49.8 mmol) phenothiazine, 25.0 g (99.6 mmol) 98% 2,4,6-trimethyl-iodobenzene, 8.30 g (60.0 mmol) potassium carbonate and 0.207 g (3.26 mmol) copper The powder was heated to 180 ° C. and stirred at this temperature for 24 hours. Thereafter, excess 2,4,6-trimethyliodobenzene was distilled off. The reaction mixture was mixed with 300 ml of water and stirred overnight. This suspension was filtered, washed with hot water until neutral and dried at 80 ° C. under reduced pressure. The crude product (16.6 g) was heated to boil for 2 hours in 500 ml of ethanol under reflux and then diluted with 200 ml of water. The precipitate was filtered off with suction, dried at 80 ° C. (10.5 μg) under reduced pressure and dissolved in 150 ml of toluene. This solution was filtered through silica gel. After the filtrate was concentrated, 7.22 g of light brown fine crystals having a melting point of 192-200 ° C were obtained.

b) 10- Mesitylphenothiazine  5,5- Dioxide

A solution of 1.50 g (4.73 mmol) of 10-mesitylphenothiazine in 55 ml of methylene chloride is mixed with 2.80 g (11.4 mmol) of 70% m-chloroperbenzoic acid at room temperature for 8 hours at 20-25 ° C. Stirred. This solution was successively extracted twice in each case with 20 ml of 10% potassium hydroxide solution, 20 ml of 5% hydrochloric acid and 15 ml of saturated sodium bicarbonate solution. This solution was filtered through silica gel. After concentration of the filtrate, 1.43 g (86% theoretical) of beige microcrystals having a melting point of 242-246 ° C. were isolated in analytical pure form. Recrystallization in acetic acid produced colorless crystals which melted at 240-246 ° C. The solution of this material in chloroform fluoresced at λ = 349, 370 μs (S) μs nm.

Example  30: 1,3,5- Phenylene -10,10 ', 10 "-tris (phenothiazine 5,5- Dioxide )

a) 1,3,5- Phenylene -10,10 ', 10 "- Tris (Phenothiazine)

30.19 g (150 mmol) of phenothiazine are added to a suspension of 6.00 g (150 mmol) of sodium hydride (60% dispersion in paraffin oil) in 150 ml of anhydrous dimethylformamide while stirring at room temperature. Among them, the reaction temperature was raised to 40 ℃. After the end of hydrogen evolution (approximately 20 minutes), a solution of 6.20 g (46.0 mmol) of 98% 1,3,5-trifluorobenzene in 10 ml of dimethylformamide was added dropwise to the reaction solution within 15 minutes. . The reaction solution was then first heated at 80 ° C. for 2 hours and then at 100 ° C. for 16 hours. After cooling to room temperature, the reaction solution was precipitated in 500 ml of ice water. The precipitate was filtered off with suction, washed with hot water until neutral and then dispersed in 500 ml of methanol. This suspension was heated to boiling for 1 hour under reflux. After cooling to room temperature, the solid was filtered off with suction, washed with methanol and dried at 50 ° C. under reduced pressure. 24.80 g of solid were obtained, which were heated and boiled under reflux for 1 hour in ethyl acetate. After cooling to room temperature, the solid was filtered off with suction, washed with ethyl acetate and heated to boiling once more under reflux in ethyl acetate for 1 hour. After cooling to room temperature, the solid was filtered off with suction, washed with ethyl acetate and dried at 80 ° C. under reduced pressure. 23.34 g (76% theoretical) of a light gray solid having a melting point of 264-268 ° C were obtained.

b) 1,3,5- Phenylene -10,10 ', 10 "-tris (phenothiazine 5,5- Dioxide )

A solution of 6.70 g (10.0 mmol) of 1,3,5-phenylene-10,10 ', 10 "-tris (phenothiazine) in 180 ml of methylene chloride was 70% of 22.19 g (90.0 mmol) at room temperature. Partially mixed with m-chloroperbenzoic acid and stirred for 24 hours at 20-25 ° C. The reaction mixture was concentrated to dryness and then mixed with 150 ml of hot water and 46 ml of 10% potassium hydroxide solution. Filtration with suction, washing with hot water until neutral and drying under reduced pressure at 80 ° C. 7.63 g of beige microcrystals having a melting point> 360 ° C. were obtained.

Example  31: 4- (5,5- Dioxofenothiazine -10 days) Phenyl Benzoate

a) 10- (2- Hydroxyphenyl Phenothiazine

35.9 μg (180 μmol) phenothiazine, 44.5 μg (198 μmol) 98% 4-iodophenol (same 2-iodophenol can be used), 29.9 μg (216 μmol) potassium carbonate and 0.75 μg (12 mmol) of copper powder was heated to 198 ° C. and stirred at this temperature for 3.5 hours. The reaction melt was cooled to 140 ° C. and then mixed with 150 ml of water within 3 minutes, in which the reaction mixture solidified. After cooling with dry ice, the solids were isolated, ground in a mortar and mixed with 150 ml of water. This suspension was steam distilled to remove excess iodophenol. The solid was then filtered off with suction and washed with water. The water-moist solid was suspended in 400 mL ml of ethanol, dried overnight at room temperature, then filtered off with suction, washed with ethanol and dried at 80 ° C. under reduced pressure. The crude product (16.6 μg) was heated to boil for 2 hours in 500 mL of ethanol under reflux and then diluted with 200 mL of water. The precipitate was filtered off with suction, dried at 80 ° C. under reduced pressure (10.5 g) and dissolved in 150 ml of toluene. This solution was filtered through silica gel. After the filtrate was concentrated, 7.22 g of light brown fine crystals having a melting point of 192-200 占 폚 were obtained.

b) 2- (phenothiazine-10-day) Phenyl Benzoate

16.0 g (114 mmol) of benzoyl chloride was added dropwise to a solution of 4.00 (g (13.7 mmol) of 10- (2-hydroxyphenyl) phenothiazine in 24 ml of pyridine within 30 minutes with stirring at 0-5 ° C. After stirring for 2 hours at room temperature, the reaction solution was heated to 60-65 ° C. and stirred at this temperature for 15 minutes. After cooling to room temperature, the suspension was then stirred overnight. After addition of 300 mL of ice water, the suspension was slowly mixed with 19 mL of concentrated hydrochloric acid (pH 0.9) and stirred for 1 hour. The suspension was filtered through glass frit. The residue was washed with 2 L of water until neutral and dried at 60 ° C. under reduced pressure. 2.87 g (53% theory) of colorless microcrystals having a melting point of 144-148 ° C. was obtained.

c) 2- (5,5- Dioxofenothiazine -10 days) Phenyl Benzoate

A solution of 1.32 g (3.33 mmol) of 2- (phenothiazin-10-yl) phenyl benzoate in 50 ml of methylene chloride was mixed with 1.81 g (7.33 mmol) of 70% m-chloroperbenzoic acid at room temperature, Stir at 20 ° C. for 24 hours. This solution was concentrated to dryness under reduced pressure. The residue was triturated in 50 mL ml of water. The suspension was heated to 80 ° C. and stirred for 20 minutes after the addition of 4.5 mL of 10% potassium hydroxide solution. The beige solid was filtered off with suction while hot, washed with hot water and dried at 70 ° C. (1.285 μg). A solution of this solid in 22 ml ml of methylene chloride was filtered through MN 60 silica gel, which was then washed with a mixture of 100 parts methylene chloride and 1 part methanol. After the filtrate was concentrated, the residue was recrystallized from acetic acid. 0.93 g (65% theory) of colorless microcrystals having a melting point of 228-232 ° C was obtained.

Example  32: 10- (2- Hydroxyphenyl Phenothiazine 5,5- Dioxide

A solution of 1.50 g (5.14 mmol) of 10- (2-hydroxyphenyl) phenothiazine in 50 ml of methylene chloride was mixed with 2.79 g (11.31 mmol) of 70% m-chloroperbenzoic acid at room temperature and Stir for 5.5 hours. This solution was concentrated to dryness under reduced pressure. The residue was triturated in 100 ml of water. The suspension was heated to 80 ° C. and stirred for 20 minutes after the addition of 7.5 μl of 10% potassium hydroxide solution. The solid was filtered off with suction while hot, washed with hot water and dried at 70 ° C. (1.45 μg). The beige solid was recrystallized twice from 42 kml of acetic acid each time. 0.92 g (55% of theory) of colorless microcrystals were obtained, which were melted at 282-287 ° C.

Example  33: 4- (5,5- Dioxofenothiazine -10 days) Phenyl Benzoate

a) 4- Iodophenyl  Benzyl ether

A reaction mixture consisting of 21.40 g (95.3 mmol) of 98% 4-iodophenol, 20.73 g (150 mmol) of potassium carbonate and 250 ml of acetone in 12.19 g (95.3 mmol) of 99% benzyl chloride was heated to reflux Heated to boiling for 30 minutes. After cooling to room temperature, the reaction mixture was filtered. The filtrate was concentrated and then cooled in an ice bath, in which a solid precipitated. It was removed with a blue band filter and then dried. The crude product (23.22 g) was recrystallized from 70 ml of ethanol. 17.20 μg (58% theory) of colorless microcrystals having a melting point of 61-62 ° C. (lit. 62 ° C.) were obtained.

b) 10- (4- Benzyloxyphenyl Phenothiazine

5.56 g (27.9 mmol) of phenothiazine, 8.65 g (27.9 mmol) of 4-iodophenyl benzyl ether, 4.64 (g (33.5 mmol) of potassium carbonate and 0.116 1.8g (1.82 mmol) of copper powder heated to 190 ° C And stirred at this temperature for 24 hours. The reaction melt was cooled to 110 ° C., then diluted with 200 μl ml of toluene and stirred at 112 ° C. for 1 hour. This solution was filtered hot. The filtrate cooled to room temperature was purified on silica gel in toluene. Beige crude product (6.52 g) was recrystallized from 125 ml of ethanol. 4.79 g (45% of theory) of beige microcrystals having a melting point of 144-146 ° C. were obtained.

c) 10- (4- benzyloxyphenyl ) phenothiazine 5,5 - dioxide

A solution of 4.60 μg (12.1 μmol) of 10- (4-benzyloxyphenyl) phenothiazine in 130 μm of methylene chloride was mixed with 6.53 μg (26.5 μmol) of 70% m-chloroperbenzoic acid at room temperature and Stir for 3 hours. This solution was concentrated to dryness under reduced pressure. The residue was triturated in 150 ml of water. This suspension was heated to 80 ° C. and stirred for 20 minutes after the addition of 14 μl of 10% potassium hydroxide solution. The solid was filtered off with suction while hot, washed with hot water and dried at 100 ° C. 4.78 g (96% theoretical) of a beige solid having a melting point of 203-208 ° C. was obtained. For removal of the methylene chloride residue, 0.96 μg of solid was sublimed at 200 ° C. under high vacuum. 0.78 ng of analytical pure colorless microcrystals were obtained, which were melted at 204-208 ° C.

d) 10- (4- Hydroxyphenyl Phenothiazine 5,5- Dioxide

3.10 μg (7.50 μmol) of 10- (4-benzyloxyphenyl) phenothiazine 5,5-dioxide, 2.30 μg (35.7 μmol) of 98% ammonium formate and 7.5 μg of 10% palladium on activated carbon under reflux Heated in acetone for 1 hour. After cooling to room temperature, the solution was filtered. The filtrate was concentrated and stirred overnight after addition of 10 μml of methanol. The solid was filtered off with suction, washed with methanol and dried at 110 ° C. in a vacuum drying cabinet. Analytical pure light gray fine crystals of 1.47 g (61% in theory) having a melting point of 308-311 ° C. were obtained.

e) 4- (5,5- Dioxofenothiazine -10 days) Phenyl Benzoate

0.68 g (6.68 mmol) triethylamine and 0.34 2.4g (2.44 mmol) benzoyl chloride in 0.72 g (2.22 mmol) 10- (4-hydroxyphenyl) -phenothiazine 5,5 in 120 ml acetonitrile -Added to a solution of dioxide. After stirring for 45 minutes at room temperature, the solvent was distilled off. The residue was triturated in 100 μml of hot water and stirred at 75 ° C. for 30 minutes. The solid was filtered off with suction while hot, washed with hot water and dried in a forced draft drying cabinet at 120 ° C. 0.87 g (92% of theory) colorless microcrystals having a melting point of 233-235 ° C were obtained.

Example  34: 10- (3,5- Difluorophenyl Phenothiazine 5,5- Dioxide

a) 10- (3,5- Difluorophenyl Phenothiazine

10.07 g (50.0 mmol) of phenothiazine is added to a suspension of 2.00 g (50.0 mmol) of sodium hydride (60% dispersion in paraffin oil) in 100 ml of anhydrous dimethylformamide while stirring at room temperature. It was added within 10 minutes, during which the reaction temperature was raised to 32 ° C. After termination of hydrogen evolution (approximately 20 minutes), a solution of 7.41 g (55.0 mmol) of 98% 1,3,5-trifluorobenzene in 50 ml of dimethylformamide was added to the reaction solution heated to 85 ° C. for 15 minutes. It was added dropwise within. Thereafter, the reaction solution was stirred at this temperature for 24 hours. After cooling to room temperature, the reaction solution was slowly precipitated in 500 ml of ice water. After addition of 18 g sodium chloride, the aqueous suspension was stirred for 2 hours and then filtered. The residue was washed with water and dried. The solid was suspended in 200 ml of hexane and heated at reflux for 1 hour. After cooling to room temperature, the suspension was filtered. The filtrate was concentrated to dryness under reduced pressure. The residue (7.00 g) was stirred in 230 ml of a mixture of 40 parts hexanes and 1 part ethyl acetate and filtered. The filtrate was chromatographed on silica gel using an eluent consisting of 40 parts hexane and 1 part ethyl acetate. After removal of the solvent, the residue was dried at 80 ° C., 1.8 × 10 ⁻⁵ mbar, in which some of this material sublimed. Solids remaining in the vessel were recrystallized from 40 ml of ethanol. 1.18 g (7.6% in theory) of analytical pure colorless microcrystals having a melting point of 111-115 ° C were obtained.

b) 10- (3,5- Difluorophenyl Phenothiazine 5,5- Dioxide

A solution of 1.40 g (4.50 mmol) of 10- (3,5-difluorophenyl) phenothiazine in 40 ml of methylene chloride was mixed with 2.46 g (10.0 mmol) of 70% m-chloroperbenzoic acid at room temperature And stirred at room temperature for 2 hours. This solution was concentrated to dryness under reduced pressure. The residue was stirred at 100 ° C. in water at 50 ° C. for 30 minutes. The suspension was mixed with 7.5 mL of 10% potassium hydroxide solution, stirred for 30 minutes and then filtered. The solid was filtered off with suction while hot, washed with hot water and dried at 80 ° C. Beige solid (1.54 g) was recrystallized twice from acetic acid. After drying at 130 ° C. under high vacuum, 0.73 μg (47% theory) of analytical pure colorless microcrystals were obtained, which were melted at 255-258 ° C.

Example  35: 10- (2- Pyridyl Phenothiazine 5,5- Dioxide

a) 10- (2- Pyridyl Phenothiazine

4.46 μg (22.4 μmol) of phenothiazine, 9.36 μg (47.6 μmol) of 98% 2-iodopyridine, 3.72 μg (26.9 μmol) of potassium carbonate and 0.093 μg (1.5 μmol) of copper powder at 192 ° C. Heat and stir at this temperature for 24 hours. The reaction melt was cooled to 100 ° C., then slowly diluted with 200 μl of ethanol and heated to boiling for 1 hour under reflux. After cooling to room temperature, the reaction mixture was filtered, which left a tacky paste, which was dissolved in 100 μml of methylene chloride. This methylene chloride solution was purified on silica gel to give two fractions. The second fraction was concentrated to dryness. 2.55 g (41% theory) of beige fine crystals having a melting point of 107-109 ° C (lit .: 109-110 ° C) was obtained.

b) 10- (2- Pyridyl Phenothiazine 5,5- Dioxide

A solution of 2.20 μg (7.96 mmol) of 10- (2-pyridyl) phenothiazine in 80 mL ml of methylene chloride was mixed with 4.32 μg (17.5 mmol) of 70% m-chloroperbenzoic acid at room temperature while cooling and Stirred for 2 h. This solution was concentrated to dryness under reduced pressure. The residue was triturated in 200 ℃ ml of water at 70 ° C and mixed with 10 ml of 10% KOH. After stirring for 30 minutes, the suspension was filtered. The residue was washed with hot water and dried at 50 ° C. under reduced pressure. A colorless solid (1.87 g) was dissolved in 20 ml of a mixture of 99 parts of methylene chloride and 1 part of methanol and purified on silica gel. The purified solution was concentrated to dryness. After the residue was dried at 70 ° C. under reduced pressure, it was recrystallized from 10 ml of acetic acid. Analytical pure colorless microcrystals of 1.09 ng (44% theoretical) were obtained, which were melted at 186-190 ° C. After extended standing of the filtrate in acetic acid at room temperature, another 0.32 g of colorless microcrystals having a melting point of 184-188 ° C precipitated (total yield: 57%).

Example 36: 10- [4-(N- Phenyl -2- Benzimidazolyl ) Phenyl ] Phenothiazine 5,5- Dioxide

a) N- Phenyl -2- (4- Iodophenyl ) Benzimidazole

37.47 μg (136 μmol) of 97% 4-iodobenzoyl chloride and 12.82 μg (68.2 μmol) of 98% o-aminodiphenylamine were heated to 100 ° C., in which a stirrable melt formed from 85-90 ° C. It became. Once gas evolution was complete (5 minutes), the melt solidified. The reaction mixture was kept at 100 ° C. for an additional 3 hours. After cooling, it was mixed with 100 mL ml of ethanol while stirring. The precipitate was filtered off with suction, washed with ethanol and again stirred in 400 mL of ethanol. This suspension was heated to 75 [deg.] C., whereby a solution was formed, which was adjusted to pH # 8 with 29 [mu] ml of 25% ammonia. After cooling to 5-10 ° C., the precipitate was filtered off with suction, washed with cold ethanol and dried at 75 ° C. in a vacuum drying cabinet. 18.37 g (68% theory) of light gray fine crystals having a melting point of 178-181 ° C. were obtained.

b) 10- [4- (N- Phenyl -2- Benzimidazolyl ) Phenyl ] Phenothiazine

7.77 g (39.0 mmol) phenothiazine, 17.00 g (42.9 mmol) N-phenyl-2- (4-iodophenyl) benzimidazole, 6.47 g (46.8 mmol) potassium carbonate and 0.162 g (2.54 mmol) ) Copper powder was heated to 195-200 ° C. and stirred at this temperature for 19 hours. The reaction melt was cooled to 130 ° C. and then diluted with 100 mL ml of ethanol. After heating for 30 minutes under reflux, the solution was filtered hot. The suspension was concentrated to dryness and then mixed with 150 μml of methylene chloride. After filtration, the filtrate was filtered through silica gel. 11.03 g of beige microcrystals were obtained.

c) 10- [4- (N- Phenyl -2- Benzimidazolyl ) Phenyl ] Phenothiazine 5,5- Dioxide

A solution of 6.14 g of 10- [4- (N-phenyl-2-benzimidazolyl) phenyl] phenothiazine in 180 ml of methylene chloride was obtained at 7.17 g (28.9 mmol) of 70% m-chloroperbenzoic acid at room temperature. Was mixed with cooling and stirred at room temperature for 1 hour. This solution was mixed with 60 μl of 10% KOH. After methylene chloride was removed, the suspension was diluted with 100 ml of hot water. The precipitate was filtered off with suction, washed with hot water and dried at 80 ° C. under reduced pressure. The crude product (4.82 g) was recrystallized from 48 ml of acetic acid. 3.02 g (46% theoretical) of beige fine crystals having a melting point of 286-288 ° C were obtained.

Example 37: 10- Mesityl -3- (2- {4 '-[2- (10- Mesityl -5,5- Dioxofenothiazine -3-yl) -vinyl] biphenyl-4-yl} vinyl) phenothiazine 5,5- Dioxide

a) 10- Mesitylphenothiazine -3- Carbaldehyde

3.66 μg (23.6 μmol) of 99% phosphorus oxychloride at 20 ° C. with stirring and ice-cooling at 5.00 μg (15.8 μmol) of 10-methylphenothiazine and 3.23 μg (23.6 μmol) of 99 μg in 5 μg of o-dichlorobenzene To the solution of% N-methylformanilide was added dropwise within 15 minutes. After stirring at 20 ° C. for 30 minutes, the reaction solution was heated to 70 ° C. and maintained at this temperature for 4 hours. The reaction solution was mixed with a solution of 16 kg sodium acetate in 35 kml of water within 5 minutes. After stirring for 1 hour at 70, N-methylformanilide and o-dichlorobenzene were removed by steam distillation. 250 ml of methylene chloride was added to the distillation base. The organic phase was transferred and filtered through silica gel. The filtrate was concentrated and dried at 40 ° C. under reduced pressure. An analytical pure, greenish powder of 5.05 g (93% theoretical) having a melting point of 136-140 ° C. was obtained.

b) 10- Mesityl -5,5- Dioxofenothiazine -3- Carbaldehyde

A solution of 4.00 g (11.6 mol) of 10-mesitylphenothiazine-3-carbaldehyde in 150 ml of methylene chloride was mixed in part with 6.28 g (25.5 mmol) of 70% m-chloroperbenzoic acid at room temperature and Stirred for 3 h. This solution was concentrated to dryness under reduced pressure. The residue was dissolved in 25 ml of a mixture of 98 parts methylene chloride and 2 parts methanol and purified by column chromatography on silica gel. The solution was concentrated to dryness and dried at 50 ° C. under reduced pressure. 2.75 g (63% theory) of yellowish microcrystals were obtained, which were melted at 194-197 ° C.

c) 10- Mesityl -3- (2- {4 '-[2- (10- Mesityl -5,5- Dioxofenothiazine -3-yl) vinyl] biphenyl-4-yl} vinyl) phenothiazine 5,5- Dioxide

0.93 g (8.1 mmol) of potassium tert-butoxide followed by 2.70 g (7.16 mmol) of 10-mesityl-5,5-dioxophenothiazine-3-carbaldehyde (Example 35 b) is a molecule 1.63 g (3.58 mmol) of diethyl [4 '-(diethoxyphosphorylmethyl) biphenyl-4-ylmethyl] phosphonate in 40 ml of dimethyl sulfoxide dried over a sieve (US 3,984,399, Example 2, 29 stages, lines 58-66) were added at room temperature with stirring under nitrogen. After stirring for 4 hours at room temperature, the reaction solution was diluted with 200 ml of methanol and stirred for a further 1 hour. The precipitate was filtered off, washed with 100 ml of methanol, stirred again in 300 ml of methanol, filtered again and dried at 35 ° C. under reduced pressure. The crude product (2.90 g) was recrystallized twice from dimethylformamide and once from chlorobenzene. The crystals were filtered off with suction, washed successively with chlorobenzene and ethanol, filtered off with suction and dried at 80 ° C. under reduced pressure. After removing the solvent residue under high vacuum (2 × 10 ⁻⁵ mbar) at 250 ° C., 0.98 g (30% theoretical) of analytical pure, luminous yellow microcrystals having a melting point> 350 ° C. were obtained, The solution in chloroform fluoresced at λ = 456, 485 (S), 522 (S) nm.

Example  38: 10- (2- Thiophenyl Phenothiazine 5,5'- Dioxide

a) 10- (2- Thiophenyl Phenothiazine

42 μg of phenothiazine, 9.1 μg (42 μmol) of 98% 2-iodothiophene, 7.0 μg (51 μmol) of potassium carbonate and 0.18 μg (2.8 μmol) of copper powder to 140 ° C. And stirred at this temperature for 7 hours. The reaction melt was cooled down, mixed with 200 mL ml of ethanol, heated to reflux and hot filtered. The residue was washed twice with ethanol. This ethanol solution was concentrated and after column chromatography (eluant: 2: 5 ethyl acetate / cyclohexane), a valuable product of 3.13 lg was obtained, which was used directly in the subsequent reaction step b).

b) 10- (2- Thiophenyl Phenothiazine 5,5'- Dioxide

3.13 g (11.1 mmol) of 10- (2-thiophenyl) phenothiazine from reaction step a) was dissolved in 100 ml of methylene chloride. At 0-5 ° C., 5.52 μg (22.4 μmol) of 77% m-chloroperbenzoic acid was added in portions. The reaction solution was stirred at room temperature for 2 hours. The reaction mixture was concentrated and the residue was dissolved in 250 μm ml of methylene chloride. The organic phase was washed three times with 20 μl of 10% potassium hydroxide solution each time and five times with 50 μl of demineralized water each time. After column chromatography (eluant: methylene chloride), a valuable product was obtained, which was further purified by crystallization from acetic acid and subsequent sublimation. 0.34 g (10% theory) of colorless microcrystals having a melting point of 230-234 ° C was obtained.

Example 39: 2,5- (1,4- Dimethoxyphenylene ) -10,10'- Vis (Phenothiazine) 5,5'- Deoxy De

a) 2,5- (1,4- Dimethoxyphenylene ) -10,10'- Vis (Phenothiazine)

This preparation is described in K. Okada et al., J. Am. Chem. Soc. 1996, 118, 3047-3048.

0.8 μg (4.0 mmol) phenothiazine, 0.88 μg (2.2 mmol) 97% 1,4-diiodo-2,5-dimethoxybenzene, 0.66 μg (4.8 mmol) potassium carbonate and 0.016 μg (0.25 μg) mmol) of activated copper powder was heated to 140 ° C. in DMSO (10 μml) and stirred at this temperature for 15 hours. After cooling the reaction mixture to room temperature, 30 [mu] ml of methylene chloride was added and the suspension was filtered. This methylene chloride solution was washed three times with 25 [mu] ml of 0.1 mol of hydrochloric acid each time, dried and concentrated. 0.99 g of target compound was obtained as a colorless solid.

b) 2,5- (1,4- Dimethoxyphenylene ) -10,10'- Vis (Phenothiazine) 5,5'- Dioxide

0.43 g (0.81 mmol) of 2,5- (1,4-dimethoxyphenylene) -10,10'-bis (phenothiazine) from reaction step a) was dissolved in 15 ml of methylene chloride. After 1 hour of stirring at room temperature, 0.56 μg (3.2 mmol) of 77% m-chloroperbenzoic acid was added in portions. The reaction solution was stirred at room temperature for 24 hours, in which solid precipitated. The suspension was concentrated and the residue in demineralized water was adjusted to pH 12 with 10 ml of 10% sodium hydroxide solution, stirred at 70 ° C. for 1 hour and then filtered. The residue was washed with hot water and dried at 80 ° C. under reduced pressure. 0.20 생성물 g (41%) of valuable product was obtained.

Example  40: OLED Manufacture

OLEDs having the following layer structure were prepared by vapor deposition of individual layers: ITO / NPD (40 nm) / 3,7-bis (2,2-diphenylvinyl) -10-methylphenothiazine 5,5 -Oxide (Example 13) (40 nm) / BCP (6 nm) / LiF (1 nm) / aluminum.

NPD = 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl

BCP = 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline

LiF = lithium fluoride

The OLED has a maximum photometric efficiency of 2.7 cd / A at 4µV and a maximum illumination density of 5750 cd / m at 9V. The maximum intensity of electric field emission was at 455 nm.

Example  41: OLED Manufacturing (holes and Exciton  As a blocker mPTO2 )

OLEDs having the following layer structure were prepared by vapor deposition of the individual layers: ITO / DPBIC (28 nm) / ester: CN-PMIC (33%) (20 nm) / mPTO2 (Example 5) (5 nm) / TPBI (40 nm) / LiF (0.7 nm) / Aluminum.

DPBIC (whole conductor and exciton blocker) =

Ester (matrices for emitters) =

CN-PMIC =

mPTO2 (hole and excitone blocker) = 1,3-phenylene-10,10'-bis (phenothiazine 5,5-dioxide)

TPBI (electron conductor) = 1,3,5-phenylene-2,2 ', 2 "-tris (1-phenylbenzimidazole)

LiF = lithium fluoride

The OLED has the following electro-optical data:

Emission 464 nm CIE chromaticity coordinates (x, y) 0.15; 0.15 Maximum metering efficiency 15.1 cd / A Metering efficiency at 100 cd / m ² (600 cd / m ² ) 14.4 cd / A (12.1 cd / A) Power efficiency 11.1 lm / W External quantum yield 12.1% Brightness 2000 cd / m ²

Claims (22)

Use of compounds of formula (I) as emitter materials or hole and exciton blockers in organic light emitting diodes: Formula I

In the above formula, X is S, SO ₂ , O, SO; R ¹ is H, alkyl, aryl, heteroaryl; or A group of formula IV or formula V; Formula IV

Formula V

R ² , R ³ are each independently H, alkyl, aryl, NR ²² R ²³ or COR ³¹ , wherein R ² and R ³ are not H at the same time, or At least one of the R ² or R ³ radicals is a radical of the formula II; or R ² , R ³ are each independently H, alkyl, aryl, NR ²² R ²³ , wherein R ² and R ³ are not H at the same time, or At least one of the R ² or R ³ radicals is a radical of the formula (II) wherein the additional R ² or R ³ radicals have the same definition or are H, alkyl, aryl, NR ²² R ²³ , preferably further R ² or R ³ radicals are likewise radicals of formula II, or Formula II

One of the R ² or R ³ radicals is a radical of formula III wherein the further R ² or R ³ radicals are H, alkyl, aryl, NR ²² R ²³ ; Formula III

R ⁴ , R ⁵ , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ are Each independently is alkyl, aryl, alkenyl, alkynyl or alkylaryl; R ¹⁷ is halogen, alkoxy, alkyl, aryl, alkenyl, alkynyl or alkylaryl; m, n are each 0, 1, 2 or 3, preferably 0 or 1, more preferably 0; o, p, q, r, s, t, u, v, w are each 0, 1, 2, 3 or 4, preferably 0 or 1, more preferably 0; z is 1 or 2; R ⁶ , R ⁷ are each independently H, alkyl, aryl, alkenyl, alkynyl, alkylaryl, alkoxy, aryloxy or NR ²² R ²³ ; R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are each independently H, alkyl, aryl, alkenyl, alkynyl or alkaryl; R ¹² is H, alkyl or aryl; R ²² , R ²³ are each independently H, alkyl, aryl, or R ²² and R ²³ together form a cyclic radical; Y, Z, W are S, SO ₂ , O, SO; Ar is arylene; R ³¹ is H, alkyl or aryl. The use according to claim 1, wherein an emitter material of formula (I) or a hole or exciton blocker is used wherein the symbols and radicals are each defined as follows: X is S or SO ₂ ; R ¹ is H, methyl, ethyl, unsubstituted phenyl or 4-alkoxyphenyl; Or phenyl, 4-methoxyphenyl, thienyl or pyridyl substituted with one OH, OC (O) Ph, OCH ₂ Ph or N-phenylbenzimidazolyl group, two F radicals, three CH ₃ groups , or A group of formula IV or formula V; Formula IV

Formula V

R ² , R ³ are each H, unsubstituted phenyl, 1-naphthyl, 2-naphthyl or NR ²² R ²³ or CHO, wherein at least one of the R ² or R ³ radicals is unsubstituted phenyl, 1-naphthyl , 2-naphthyl or NR ²² R ²³ , or R ² and R ³ are each a group of formula II, or Formula II

R ² is H and R ³ is a group of formula III; Formula III

m, n, o, p, q, r, s, t, u, v and w are each 0, 1 or 2, preferably 0; z is 1 or 2; R ⁶ and R ⁷ are each unsubstituted phenyl; R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are each H; R ¹² is H, methyl, ethyl, unsubstituted phenyl or 4-alkoxyphenyl or phenyl substituted with three CH ₃ groups; R ¹⁷ is alkyl, alkoxy, preferably methoxy; R ²² and R ²³ are each aryl; Y, Z, W are each S or SO ₂ ; Ar is phenylene, naphthylene or biphenylene. Use according to claim 1 or 2, wherein the emitter material of formula (I) is selected from the group consisting of compounds of formula (Ia), (Ib), (Ic), (Id), (Ie), (If) and (Ig). Formula Ia

Formula Ib

Formula Ic

Chemical Formula Id

Formula Ie

Formula If

Formula Ig

In the above formula, X, Y, Z, W and Q are each independently S or SO ₂ ; R ¹ , R ¹² are each H, methyl, ethyl or unsubstituted phenyl; R ² , R ³ are each H or unsubstituted phenyl, wherein at least R ² or R ³ is unsubstituted phenyl; R ⁶ is methyl or unsubstituted phenyl; R ¹⁷ is methoxy; s is 0 or 2, where when s = 2 the substituents are preferably arranged in 2- and 5-positions; Ph is unsubstituted phenyl. The method of claim 1 or 2, wherein the emitter material of formula I is selected from the group consisting of compounds of formulas Ih and Ii, Formula Ih

Formula Ii

[In the formula, X and Y are each independently S or SO ₂ ; R ¹ is phenyl substituted with one OH, OC (O) Ph, OCH ₂ Ph or N-phenylbenzimidazolyl group, three CH ₃ groups or two F radicals, 4-methoxyphenyl, thienyl or Pyridyl; R ² is H; R ³ is H or CHO; Preferably H, R ¹² is phenyl substituted with three CH ₃ groups] The hole and exciton blocker of formula (I) are selected from the group consisting of compounds of formula (Ia), (Id), (Ie), (Ig) and (Ih), particularly preferably selected from compounds of formula (Ia) and (Ih). Use according to claim 1 or 2, wherein the hole or exciton blocker of formula (I) is selected from the group consisting of compounds of formulas (Ia), (Id), (Ie), (Ig) and (Ih). Formula Ia

Chemical Formula Id

Formula Ie

Formula Ig

Formula Ih

In the above formula, X, Z and Q are each independently S or SO ₂ ; R ¹ is substituted with H, methyl, ethyl or unsubstituted phenyl, or one OH, OC (O) Ph, OCH ₂ Ph or N-phenylbenzimidazolyl group, three CH ₃ groups or two F radicals Phenyl, 4-methoxyphenyl, thienyl or pyridyl; R ² , R ³ are each H or unsubstituted phenyl, wherein at least R ² or R ³ is unsubstituted phenyl, or R ¹ is one of OH, OC (O) Ph, OCH ₂ Ph, or N- phenyl-benzimidazolyl group, a 3 CH ₃ group or a 2-substituted phenyl radical F, the 4-methoxyphenyl, thienyl Or pyridyl, R ² is H; R ³ is H or CHO; Preferably H. An organic light emitting diode comprising a light emitting layer, The light emitting layer comprises at least one emitter material of formula (I) according to any one of claims 1 to 4. 5. Light-emitting layer comprising at least one emitter material of formula I according to claim 1. 5. Light-emitting layer composed of at least one emitter material of formula I according to claim 1. An organic light emitting diode comprising the light emitting layer according to claim 7. An organic light emitting diode comprising a blocking layer for holes and excitons, The blocking layer for holes and excitons comprises at least one compound of formula (I) according to any one of claims 1, 2 or 5. Still image display devices such as computers, televisions, visual display units in printers, kitchen appliances and advertising panels, lighting, information panels, mobile phones, laptops, digital cameras, vehicles and buses; A device selected from the group consisting of mobile video display devices such as video display devices on a destination display on a train. Phenothiazine S, S-dioxide derivatives selected from the group consisting of compounds of formulas XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI and XXII: Formula XIV

Formula XV

Formula XVI

Formula XVII

Formula XVIII

Formula XIX

Formula XX

Formula XXI

Formula XXII

In the above formula, R ¹ , R ¹² are each H, Me, Et or unsubstituted phenyl; R ^{1 '} is 4-methoxyphenyl or mesityl; R ⁶ is Me or unsubstituted phenyl; R ¹⁷ is methoxy; s is 0 or 2, where when s = 2 the substituents are preferably arranged in 2- and 5-positions; Ph is unsubstituted phenyl; Naphthyl is 1- or 2-naphthyl; R ²⁸ is H or -CHO. Phenothiazine derivatives selected from the group consisting of compounds of formulas XXIII, XXIV, XXV, XXVI, XXVII, XXVIII and XXIX: Formula XXIII

Formula XXIV

Formula XXV

Formula XXVI

Formula XXVII

Formula XXVIII

Chemical Formula XXIX

In the above formula, R ¹ , R ¹² are each H, Me, Et or unsubstituted phenyl; Ph is unsubstituted phenyl; Naphthyl is 1- or 2-naphthyl; R ²⁹ , R ³⁰ are each -CHO or

to be. Phenothiazine S-oxide derivative of formula Formula XXX

In the above formula, R ¹ is H, Me, Et or unsubstituted phenyl; Naphthyl is 1- or 2-naphthyl. Phenothiazine S, S-dioxide derivatives selected from the group consisting of compounds of formulas XXXI and XXXII: Formula XXXI

Chemical Formula XXXII

In the above formula, R ¹ is phenyl substituted with one OH, OC (O) Ph, OCH ₂ Ph or N-phenylbenzimidazolyl group, three CH ₃ groups or two F radicals, 4-methoxyphenyl, 2-thi Nil or pyridyl, R ³ is H or CHO, R ¹² is phenyl substituted with three CH ₃ groups. Phenothiazine Derivatives of Formula (XXXIII) Chemical Formula XXXIII

In the above formula, R ¹ is phenyl or pyridyl substituted with one OH, OC (O) Ph, OCH ₂ Ph or N-phenylbenzimidazolyl group, three CH ₃ groups or two F radicals, R ³ is H or CHO. A phenothiazine S, S-dioxide derivative according to claim 12 or 15, a phenothiazine derivative according to claim 13 or 16 and a phenothiazine S-jade according to claim 14 in an organic light emitting diode Use of seed derivatives. At least one phenothiazine S, S-dioxide derivative according to claim 12 or 15 and / or at least one phenothiazine derivative according to claim 13 or 16 and / or at least according to claim 14 OLED comprising one phenothiazine S-oxide derivative. At least one phenothiazine S, S-dioxide derivative according to claim 12 or 15 and / or at least one phenothiazine derivative according to claim 13 or 16 and / or at least according to claim 14 Emission layer comprising one phenothiazine S-oxide derivative. An OLED comprising the light emitting layer according to claim 19. At least one phenothiazine S, S-dioxide derivative of the formulas XIV, XVII, XIX, XXI, XXII and / or 15 according to claim 15 and / or the formulas according to claim 13 A hole- and / or excitone-blocking layer comprising at least one phenothiazine derivative of formula (XXIII) according to XXIII, XXVI, XXXVIIII, XXIX and / or 16. An OLED comprising the hole- and exciton-blocking layer according to claim 21.